Benzotriazole UV absorbers having enhanced durability

ABSTRACT

Benzotriazole UV absorbers which are substituted at the 5-position of the benzo ring by an electron withdrawing group exhibit enhanced durability and very low loss rates when incorporated into automotive coatings. This is particularly the case when the 3-position of the phenyl ring is also substituted by phenyl or phenylalkyl such as α-cumyl. Compounds where the 5-position of the benzo ring are substituted by perfluoroalkyl such as trifluoromethyl are particularly of interest for both their enhanced durability and for their excellent solubility and excellent color properties in some thermoplastic compositions when the phenyl ring is substituted at the 3-position by hydrogen or tert-alkyl.

This application is a division of Ser. No. 09/234,880, filed Jan. 21,1999, now U.S. Pat. No. 6,166,218, which is a continunaton-in-part ofapplication Ser. No. 08/961,127, filed on Oct. 30, 1997 now U.S. Pat.No. 5,977,219, which application claims the benefit under 35 USC 19(e)of U.S. application Ser. No. 08/745,146, filed on Nov. 7, 1996, andconverted into a Provisional Application by petition under 37 CFR1.53(b)(2)(ii), filed on May 23, 1997, and granted on Aug. 7, 1997.

Benzotriazole UV absorbers being substituted in the benzo ring byelectron withdrawing moieties exhibit enhanced durability and low lossrates when incorporated into automotive coatings and thermoplasticcompositions.

BACKGROUND OF THE INVENTION

The benzotriazoles have long been an important class of UV absorbers andhave gained wide commercial importance and acceptance for manyindustrial applications. The prior art is replete with references totheir manufacture and utility. However, as requirements become ever morestringent and demanding, the search for still more stable and durablebenzotriazoles continues. The gradual phase out of HAPS solvents, suchas xylene, because of environmental concerns and their replacement withnon-HAPS solvents, such as esters, ethers or ketones, and increaseddurability requirements for automotive coatings make this search moreurgent. Indeed, the automotive industry is most concerned about UVAlosses from automotive paints and coatings as seen in the publication byJ. L. Gerlock et al., Proc. 36th Annual Tech. Sym. (Cleveland CoatingSociety), May 18, 1993.

Vysokomol Soedin, Ser. A, 18(3), 553 (1976) describes the lineardependence of hydrogen bond strength and photostability inbenzotriazoles.

J. E. Pickett et al., Angew. Makromol. Chem. 232, 229 (1995) describethe photodegradation of benzotriazole UV absorbers in poly(methylmethacrylate) films. Structural variation generally caused only smalldifferences in the rates of degradation unless the substitutiondisrupted the intramolecular hydrogen bonds which are critical forstability. Pickett et al. did not test any benzotriazoles containingboth electron withdrawing and electron donating groups as in the instantinvention.

J. Catalan et al., J. Am. Chem. Soc., 114, 964 (1992) and H. J. Heller,Eur. Polymer J. Suppl. 1969, 105 both suggest that a bulky substituentsuch as tert-butyl ortho to the hydroxy group on the phenyl ring willincrease stability in highly polar systems.

The prior art leads one to the conclusion that strengthening thehydrogen bond leads to a more stable benzotriazole, but does not teachhow this can be accomplished. The instant invention disclosesbenzotriazoles which exhibit enhanced durability, but surprisingly thisenhanced durability is not always related to greater hydrogen bondstrength. Indeed, compounds with enhanced durability often have weaker,not stronger hydrogen bonds.

U.S. Pat. Nos. 4,226,763; 4,278,589; 4,315,848; 4,275,004; 4,347,180;5,554,760; 5,563,242; 5,574,166 and 5,607,987 describe selectedbenzotriazoles, substituted in the 3-position of the hydroxyphenyl ringby an α-cumyl group, which show very good durability in automotivecoatings. These benzotriazoles represent the present state of the art.The instant invention is directed at preparing benzotriazoles whichexhibit still better durability and low loss rates from the prior artbenzotriazoles.

U.S. Pat. Nos. 5,278,314; 5,280,124; 5,436,349 and 5,516,914 describered-shifted benzotriazoles. These benzotriazoles are substituted in the3-position of the phenyl ring with an α-cumyl group and at the5-position of the benzo ring by thio ethers, alkylsulfonyl orphenylsulfonyl moieties. Red-shifting the benzotriazoles is desirablefor spectral reasons. A group at the 5-position which is also electronwithdrawing provides additional benefits in low loss rates anddurability as found in the instant invention. Missing from these patentsare any alkylsulfones with seven or fewer carbon atoms. When suchsulfonyl substituents are combined with specifically α-cumyl moieties,extremely durable compounds result which, due to the bulk of the α-cumylmoiety have sufficiently low volatility to be useful in coating andother polymer systems.

The presence of an α-cumyl or phenyl group ortho to the hydroxy group onthe phenyl ring exerts a surprisingly large positive effect onbenzotriazole photostability in coatings and photographic gel systems.The magnitude of this effect, particularly when compared to a tert-butylgroup in that position, is well beyond prediction. The combination ofboth an electron withdrawing group on the benzo ring and an α-cumyl orphenyl group on the phenyl ring in the same molecule leads to extremelydesirable properties in coating systems when high UV absorber permanenceis critical.

Novel compounds meeting these parameters as being extremely stable inaggressive use environments constitute a first portion of thisinvention.

The presence of the electron withdrawing moiety at the 5-position of thebenzo ring has a powerful stabilizing effect on benzotriazoles ingeneral and is observed in other polymer systems such as polycarbonateand poly(vinyl chloride) substrates as well. However, the effect ofhaving an α-cumyl or phenyl group ortho to the hydroxy moiety on thephenyl ring is much smaller to non-existent in some polymer systems suchas polycarbonate or poly(vinyl chloride) even though critical forcoating systems as described above.

In addition to being more photostable, the compounds of this inventionare red-shifted, absorbing strongly in the 350-400 nm wavelength range.While such red-shifting is desirable in that a greater portion of the UVspectrum is absorbed, this can also introduce color if the absorptionbeyond 400 nm is significant. This can limit the use of such compounds,particularly in systems such as polycarbonate glazing applications orpresent difficulties in various pigmented systems.

It is found that the nature of the substituent ortho to the hydroxylgroup on the phenyl ring has an unexpected impact on color imparted tothe substrate by the benzotriazole. Thus, relatively subtle differencesin substitution on the phenyl ring can have a large impact on theresulting color and the applicability of the benzotriazole in specificcolor sensitive applications. There are striking differences betweenhaving hydrogen, alkyl or α-cumyl at this 3-position.

Furthermore, it is found that, when the 5-position of the benzo ring issubstituted with a trifluoromethyl group, the resulting benzotriazolenot only exhibits the same or greater enhanced stability whenincorporated into thermoplastic resins, but also imparts less color thanrelated benzotriazoles substituted at the 5-position with other electronwithdrawing moieties such as sulfonyl or carbonyl. These trifluoromethylcompounds also absorb strongly in the 350-400 nm wavelength rangedespite the low color and are extremely compatible in a wide range ofsubstrates such as acrylic resins, hydrocarbons, polycarbonates andpoly(vinyl chloride).

There are a multitude of general references to benzotriazoles having inthe 5-position of the benzo ring electron withdrawing groups such asesters, amides, sulfones and the like that are not substituted in the3-position of the phenyl ring by an α-cumyl or phenyl moiety. In many ofthese references the broadly described compounds are unexemplified andno teaching or appreciation taught of the positive effect onphotostability described in this invention. In any event, the vastmajority of these structures fall well outside the scope of instantinvention.

Perfluoroalkyl, specifically trifluoromethyl, is an ideal substituentfor the 5-position of the benzo ring. The prior art relevant to thissubstituent is very limited and exemplifies none of the instantcompounds. As a result, said prior art naturally fails to point out theimportant advantages regarding stability, color and compatibilityachievable with the 5-trifluoromethyl substituted benzotriazoles of thisinvention. The general, unexemplified references to alkyl substitutedwith halogen are acknowledged, but are clearly irrelevant to the instantinvention.

German Offen. 1,670,951 describes inter alia the use of methylene (oralkylidene) bis-benzotriazoles substituted with electron withdrawinggroups in polymeric resins. Especially useful are the asymmetricalcompounds where only one benzotriazole moiety is substituted. Suchasymmetric compounds have considerably less color.

German 116,230 provides a method of preparing benzotriazole N-oxideintermediates which can be converted into dyes and light stabilizers.The N-oxide of5-trifluoromethyl-2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole isdisclosed. This N-oxide could be reduced to the correspondingbenzotriazole which is substituted at the 5-position of the phenyl ring.However, this benzotriazole is clearly outside the scope of the instantclaims. Other related light stabilizer intermediates are genericallydisclosed in this reference, but none where ever converted to actualbenzotriazole UV absorbers. The outstanding properties of suchbenzotriazole UV absorbers clearly went undiscovered.

Japanese Hei 3-57690 claims a color developer sheet compositionscontaining salicylic acid salts and benzotriazoles. Broadly describedare benzotriazoles which may be substituted on the benzo ring withunspecified trihalomethyl. However, other benzotriazole ringsubstituents also are broadly described to include unspecified alkyl,alkoxy, aryloxy, amino, cyano, acyl, nitro and halogen. The onlybenzotriazoles named as typical examples are either unsubstituted on thebenzo ring or substituted by chlorine. The preference is for liquidcompounds. The 3-position of the phenyl ring is specified as tert-alkyl.While this reference broadly discloses a wide variety of benzotriazolederivatives in its photographic compositions many are electron donatingand produce compounds which are in photostability inferior not only tothe instant compounds, but also to standard unsubstitutedbenzotriazoles. No examples or differentiation between within thisdiverse array is seen. Further, while generic trihalomethyl isdescribed, no compounds of this description are shown or furtherdescribed in any way. Additionally, trichloro, tribromo and triiodocompounds are clearly outside the scope of the instant invention.

Japanese Sho 47-15210 describes resin compositions containing selectedbenzotriazoles substituted by a fluorinated alkyl. The genericstructures allows for a fluorinated alkyl, but not necessarilyperfluorinated alkyl, to be added to either or both the benzo or phenylrings at any position (the substituents are floating in the generialformula). Non-fluorinated substituents, one on each ring, are defined ashydrogen, halogen, hydroxy, alkyl and alkoxy with no other more specificdescription. The exemplified resins are poly(vinyl chloride),polycarbonate, ABS and nylon. Seven compounds are specificallyexemplified all outside the scope of the instant invention plus onecomposition containing 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole. Nophysical data or synthesis for any of these seven compounds are given.

The seven compounds exemplified in the Japanese reference are givenbelow:

a. 2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;

b. 5-methyl-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;

c. 5-methoxy-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;

d. 5-chloro-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;

e. 5-peroxymethoxy-2-(2-hydroxy-4-methylphenyl)-2H-benzotriazole;

f. 5-perfluorooctyl-2-(2-hydroxy-4-methylphenyl)-2H-benzotriazole; and

g.5-perfluorooctyl-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole.

There are several distinct differences between the disclosure of thisJapanese reference and the instant invention. First all the exemplifiedcompounds of the Japanese reference are substituted in the 4-position ofthe phenyl ring by groups other than hydrogen. The reference allows forsubstitution of either fluoroalkyl or fluoroalkoxy on any site on eitherring as a means of providing for an improved UV absorber. Data given inthis application shows this teaching to be inaccurate. Electronwithdrawing moities on the phenyl ring as found in a, b, c, d, and gabove, are shown to provide compounds with less durability thanunsubstituted derivatives as seen in Example 77. Spectral coverage inthe red region is also compromised as seen in Example 74. Significantly,2-(2-hydroxy-5-trifluoromethylphenyl)-2H-benzotriazole which is verysimilar to compound a above, is blue-shifted relative to benzotriazolessuch as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole as seen in Example74. Blue-shifting is undesirable since the need for coverage in the350-400 nm region is critical for UV absorbers.

An electron donating group at the 5-position of the benzo ring such asthe ether compound c above reduces stability as seen in Example 77.While the Japanese reference states fluoroalkyl or fluoroalkoxy radicalleads to enhanced stability under light, the instant invention showsthat it is the electron withdrawing nature of the group at the5-position on the benzo ring that confers greater photostability. Nosuch inference in seen in the Japanese reference, and the electrondonating ether even a fluorinated ether is counterindicated for enhancedstability.

Furthermore, all examples in the Japanese reference bear only onesubstituent on the phenyl ring and that is specifically at the4-position. The instant invention specifically claims only hydrogen atthe 4-position as substitution at the 4-position brings undesirableconsequences for the use of these compounds in many applications. Thecompound f is the closest to the instant invention, but it issubstituted by a 4-methyl group. As seen in Example 79, substitution ofthe phenyl ring by an electron donating group at the 5-positiondiminishes photostability in coatings. Pickett et al. report the sameloss of durability for such compounds in thermoplastics. The electrondonating characteristics of methyl are less pronounced, but are stillsimilar to alkoxy. The σ_(p) value, as measure of the electronic effectof substituents for aromatic methoxy substitution is −0.27 while formethyl is −0.17 (March J. “Advanced Organic Chemistry”, 2nd Ed. (1977),McGraw-Hill, New York, p 253).

While the generic disclosure of the Japanese reference overlaps formulaI of the instant application no such compound is specifically disclosedin the Japanese reference. As mentioned above, all examples of theJapanese reference are substituted at the 4-position of the phenyl ring,most contain the electron withdrawing CF₃ group at the 4-position.Compounds of the instant invention explicitly denote hydrogen at the4-position of the phenyl ring for reasons including color and stability,and expressly designate the 5-position of the benzo ring as the locationof the perfluoroalkyl moiety for reasons of stability and spectralcoverage.

U.S. Pat. Nos. 3,936,305; 4,681,905; 4,684,679; 4,684,680 and 5,108,835teach the 2,2′-methylene-bis[4-hydrocarbyl-6-(benzotriazol-2-yl)phenols]having high molar activities and low volatility. In addition UnitesStates Patent Nos. 5,292,890 and 5,360,850 teach that asymmetricalbis-benzotriazoles display higher solubility in organic non-polarsolvents that the symmetrical dimers made from the same benzotriazolemonomer.

U.S. Pat. No. 5,166,355 describes a process for making2,2′-methylene-bis[6-(benzotriazol-2-yl)-4-hydrocarbylphenol] or5,5′-methylene-bis(2-hydroxy-4-alkoxybenzophenone) usingbis(dialkylamino)methane.

Related bis-benzotriazoles of the instant invention substituted at oneor at both of the benzotriazole rings by perfluoroalkyl are unknown andprovide the same improvement to these bis-benzotriazoles as mentionedabove, namely enhanced durability and broader spectral coverage.Substitution of only one of the benzotriazole moieties in thesebis-benzotriazoles by perfluoroalkyl gives the additional advantage ofmuch lower color than the disubstituted compound, indeed nearly to thecolor of the bis-benzotriazole not substituted by perfluoroalkyl.

DETAILS OF THE DISCLOSURE

The instant invention pertains to novel benzotriazole UV absorbershaving enhanced stability and durability and a low loss rate whenincorporated into automotive coatings. These new benzotriazole UVabsorbers are also soluble in a variety of substrates includingthermoplastic polymers and often are essentially colorless even thoughabsorbing in the 350-390 nm range.

More specifically, the instant invention pertains to new benzotriazolecompounds of formula I, II, III or IV

wherein

G₁ is hydrogen or chloro,

G₂ is cyano, perfluoroalkyl of 1 to 12 carbon atoms, fluOrO, —CO—G₃,—COOG₃, —CONHG₃, —CON(G₃)₂, E₃SO— or E₃SO₂—,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms,

G₆ is perfluoroalkyl of 1 to 12 carbon atoms,

G₇ is hydrogen or perfluoroalkyl of 1 to 12 carbon atoms,

E₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms; or E₁ is alkyl of 1 to 24carbon atoms substituted by one or two hydroxy groups,

E₂ and E₂′ are independently straight or branched alkyl chain of 1 to 24carbon atoms, straight or branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by one to three alkyl of 1 to 4 carbon atoms; or E₂ and E₂′are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of2 to 18 carbon atoms substituted by one or more —OH, —OCOE₁₁, —OE₄,—NCO, —NH₂, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixtures thereof, where E₄ isstraight or branched chain alkyl of 1 to 24 carbon atoms; or said alkylor said alkenyl interrupted by one or more —O—, —NH— or —NE₄— groups ormixtures thereof and which can be unsubstituted or substituted by one ormore —OH, —OE₄ or —NH₂ groups or mixtures thereof;

n is 1 or 2,

when n is 1, E₅ is Cl, OE₆ or NE₇E₈, or

E₅ is —PO(OE₁₂)₂, —OSi(E₁₁)₃ or —OCO—E₁₁,

or straight or branched chain C₁-C₂₄alkyl which is interrupted by —O—,—S— or —NE₁₁, and which can be unsubstituted or substituted by —OH or—OCO—E₁₁, C₅-C₁₂ cycloalkyl which is unsubstituted or substituted by—OH, straight chain or branched C₂-C₁₈alkenyl which is unsubstituted orsubstituted by —OH, C₇-C₁₅aralkyl, —CH₂—CHOH-El₃ or glycidyl,

E₆ is hydrogen, straight or branched chain C₁-C2₄alkyl which isunsubstituted or substituted by one or more OH, OE₄ or NH2 groups, or—OE₆ is —(OCH₂CH₂),OH or —(OCH₂CH₂),OE₂₁ where w is 1 to 12 and E₂₁ isalkyl of 1 to 12 carbon atoms,

E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms,straight or branched chain C₃-C₁₈alkyl which is interrupted by —O—, —S—or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇ andE₈ together with the N atom are a pyrrolidine, piperidine, piperazine ormorpholine ring, or

E₅ is —X—(Z)P—Y—E₁₅

wherein

X is —O— or —N(E₁₆)—,

Y is —O— or —N(E₁₇)—,

Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to threenitrogen atoms, oxygen atoms or a mixture thereof, or isC₃-C₁₂-alkylene, butenylene, butynylene, cyclohexylene or phenylene,each substituted by a hydroxyl group,

m is zero, 1 or 2,

p is 1, or p is also zero when X and Y are —N(E₁₆)— and —N(E₁₇)—,respectively,

E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—, forms togetherwith E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ is hydrogen or methyl, andE₁₉ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ is hydrogen,C₁-C₁₂-alkyl or a group of the formula

wherein the symbols E₁, G₂, X, Z, m and p have the meanings definedabove, and E₁₆ and E₁₇ independently of one another are hydrogen,C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms, or iscyclohexyl or C₇-C₁₅aralkyl, and E₁₆ together with E₁₇ in the case whereZ is ethylene, also forms ethylene,

when n is 2, E₅ is one of divalent radicals —O—E₉—O— or—N(E₁₁)—E₁₀—N(E₁₁)—,

E₉ is C₂-C₈alkylene, C₄-C₈alkenylene, C₄alkynylene, cyclohexylene,straight or branched chain C₄-C₁₀alkylene which is interrupted by —O— orby —CH₂—CHOH—CH₂—O—E₁₄—O—CH₂—CHOH—CH₂—,

E₁₀ being straight or branched chain C2-C₁₂alkylene which may beinterrupted by —O—, cyclohexylene, or

or E₁₀ and E₁₁with the two nitrogen atoms form a piperazine ring,

E₁₄ is straight or branched chain C₂-C₈alkylene, straight or branchedchain C₄-C₁₀alkylene which is interrupted by —O—, cycloalkylene, aryleneor

where E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms or E₇ and E₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene,

E₁₁ is hydrogen, straight or branched chain C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, straight or branched chain C₂-C₁₈alkenyl, C₆-C₁₄arylor C₇-C₁₅aralkyl,

E₁₂ is straight or branched chain C₁-C₁₈alkyl, straight or branchedchain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl, C₆-C₁₆aryl or C₇-C₁₅aralkyl,

E₁₃ is H, straight chain or branched C₁-C₁₈alkyl which is substituted by—PO(OR₁₂)₂, phenyl which is unsubstituted or substituted by OH,C₇-C₁₅aralkyl or —CH₂OE₁₂,

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylaLkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms,

L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbonatoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylylene orcycloalkylidene, and

T is —SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO2—, —CO—, —CO—CO—, —CO—CH₂—CO—,—CO—E—CO—, —COO—E—OCO— or —CO—NG₅—E—NG₅—CO—,

where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12carbon atoms, or alkylene interrupted or terminated by cyclohexylene of8 to 12 carbon atoms;

G₅ is G₃ or hydrogen, and

with the proviso that when T is —SO—, —SO₂—, —SO—E—SO— or —SO₂—E—SO₂—,E₁ is not hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15carbon atoms; or when E₃ is alkyl of 1 to 6 carbon atoms, E₁ is nothydrogen or phenyl, and the sum of the carbon atoms of E₁ plus E₂ isequal to or greater than 8; and when E₃ is alkyl of 8 to 18 carbon atomsor alkenyl of 2 to 24 carbon atoms, E₁ is not hydrogen, straight orbranched chain of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbonatoms or phenylalkyl of 7 to 15 carbon atoms; or when G₂ is cyano,—CO—G₃. —CONHG₃, —CON(G₃)₂ or —COOG₃, then E₁ is phenyl or phenylalkylof 7 to 15 carbon atoms, or said phenyl or said phenylalkyl substitutedon the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or when E₁ ishydrogen, E₂ is not methyl.

Preferably, the new benzotriazole is a compound of formula I

wherein

G₁ is hydrogen,

G₂ is cyano, CF₃—, fluoro, —CO—G₃ or E₃SO₂—,

G₃ is straight or branched chain alkyl of 1 to 24 carbon atoms, straightor branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms,

E₁ is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl orsaid phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to4 carbon atoms,

E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms, straightor branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is said alkyl of 1 to 24 carbonatoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more—OH, —OCOE₁₁, —OE₄, —NCO, —NH₂, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixturesthereof, where E₄ is straight or branched chain alkyl of 1 to 24 carbonatoms; or said alkyl or said alkenyl interrupted by one or more —O—,—NH— or —NE₄— groups or mixtures thereof and which can be unsubstitutedor substituted by one or more —OH, —OE₄ or —NH₂ groups or mixturesthereof;

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms; or

is a compound of formula I wherein,

G₁ is hydrogen,

G₂ is CF₃—, fluoro or E₃SO₂—,

E₁ is hydrogen or straight or branched alkyl of 4 to 24 carbon atoms,

E₂ is as defined above, and

E₃ is straight or branched chain alkyl of 1 to 7 carbon atoms,

with the proviso that the sum of the carbon atoms in E₁ and E₂ isgreater than or equal to 8 when G₂ is E₃SO₂.

Preferably, the benzotriazole is also a compound of formula IIIA

wherein

G₁ is hydrogen,

G₂ is is CF₃— or fluoro,

E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms orphenylalkyl of 7 to 15 carbon atoms,

E₅ is —OE₆ or —NE₇E₈, or

E₅ is

—X—(Z)_(p)—Y—E₁₅

wherein

X is —O— or —N(E₁₆)—,

Y is —O— or —N(E₁₇)—,

Z is C₂-C₁₂-alkylene, C₄-C₂-alkylene interrupted by one to threenitrogen atoms, oxygen atoms or a mixture thereof, or isC₃-C₁₂-alkylene, butenylene, butynylene, cyclohexylene or phenylene,each substituted by a hydroxyl group,

m is 0, 1, 2 or 3,

p is 1, or p is also zero when X and Y are —N(E16)— and —N(E₁₇)—,respectively,

E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—, forms togetherwith E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ is hydrogen or methyl, andE₁₉ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ is hydrogen,C₁-C₁₂-alkyl or a group of the formula.

Preferably, the benzotriazole is also a compound of formula IV

wherein

G₆ is CF₃,

G₇ is hydrogen or CF₃,

E₂ and E₂′ are independently straight or branched alkyl chain of 1 to 24carbon atoms, straight or branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and

L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbonatoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylylene orcycloalkylidene.

Most preferably, the new benzotriazole is a compound of formula I

wherein

G₁ is hydrogen,

G₂ is CF₃—,

E₁ is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl orsaid phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to4 carbon atoms,

E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms, straightor branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is said alkyl of 1 to 24 carbonatoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more—OH, —OCOE₁₁, —NH₂ or —NHCOE₁₁, or mixtures thereof; or said alkyl orsaid alkenyl interrupted by one or more —O— which can be unsubstitutedor substituted by one or more —OH groups; or

is a compound of formula I wherein,

G₁ is hydrogen,

G₂ is CF₃—,

E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms orphenylaikyl of 7 to 15 carbon atoms, and

E₂ is as defined above.

Most preferably, the benzotriazole is also a compound of formula IIIA

wherein

G₁ is hydrogen,

G₂ is CF₃—,

E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms orphenylalkyl of 7 to 15 carbon atoms,

E₅ is —OE₆ or —NE₇E₈ where

E₆ is hydrogen, straight or branched chain C₁-C₂₄alkyl which isunsubstituted or substituted by one or more OH groups, or —OE₆ is—(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12 and E₂₁ isalkyl of 1 to 12 carbon atoms, and

E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms,straight or branched chain C₃-C₁₈alkyl which is interrupted by —O—, —S—or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇ andE₈ together with the N atom are a pyrrolidine, piperidine, piperazine ormorpholine ring.

Most preferably, the ben zotriazole is also a compound of formula IV

wherein

G₆ is CF₃,

G₇ is hydrogen or CF₃,

E₂ and E₂′ are independently straight or branched alkyl chain of 1 to 24carbon atoms, straight or branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and

L is methylene.

Compounds which are especially preferred are:

(a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

(c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

(d)2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol];

(e)methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2′-[4-tert-octyl-6(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];

(f)3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicacid;

(g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

(h) isooctyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

(i)5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

(j)5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole;

(k)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;

(l)5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzotriazole;

(m)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole;

(n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;

(o)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole;

(p)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(q)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

(r)5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-amylphenyl)-2H-benzotriazole;

(s)5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole;

(t)5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;

(u)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;

(v)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(w)5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(x)5-trifluoromethyl-2-(2-hydroxy-3,5di-α-cumylphenyl)-2H-benzotriazole;

(y) 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

(z) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

(aa)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;and

(bb)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-ctylphenyl)-2H-benzotriazole.

Examples of these various radicals are as follow:

When any of E₁ to E₂₁ is alkyl, such groups are, for example, methyl,ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl,2-ethylhexyl, tert-octyl, lauryl, tert-dodecyl, tridecyl, n-hexadecyl,n-octadecyl and eicosyl; when any of said radicals is alkenyl, suchgroups are, for example, allyl or oleyl; when any of said radicals iscycloalkyl, such groups are, for example, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl and cyclododecyl; when any of said radicals arephenylalkyl, such groups are, for example, benzyl, phenethyl,α-methylbenzyl and α,α-dimethylbenzyl; and when any of said radicals isaryl, they are, for example, phenyl, naphthyl, or when substituted byalkyl are, for example, tolyl and xylyl. When E₆ is alkyl substituted byone or more —O— groups and/or substituted by one or more —OH, the —OE₆moiety can be —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12and E₂₁ is alkyl of 1 to 12 carbon atoms, for example.

When E is alkylene, it is, for example, ethylene, tetramethylene,hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene,octamethylene, decamethylene and dodecamethylene; when E iscycloalkylene, it is, for example, cyclopentylene, cyclohexylene,cycloheptylene, cyclooctylene and cyclododecylene; and when E isalkylene interrupted or terminated by cyclohexylene, it is, for example,the saturated diyl radical derived from limonene, herein calleddihydrolimonenediyl.

When E is alkylene, it is, for example, ethylene, tetramethylene,hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene,octamethylene, decamethylene and dodecamethylene; when E iscycloalkylene, it is, for example, cyclopentylene, cyclohexylene,cycloheptylene, cyclooctylene and cyclododecylene; and when E isalkylene interrupted or terminated by cyclohexylene, it is, for example,the saturated diyl radical derived from limonene, herein calleddihydrolimonenediyl.

When the instant compounds contain a free carboxyl moiety where E₂ is—CH₂CH₂COOE₆ where E₆ is hydrogen, the alkali metal or amine salts ofsaid acids are also contemplated as part of this invention allowing suchUV absorbers to be used in aqueous systems due to the enhanced watersolubility of such instant compounds.

E₆, E₇ and E₈ can be the following C₃-C₁₈alkyl radicals which areinterrupted by —O—, —S—, or —NE₁₁— and can be substituted by OH:methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl,CH₃OCH₂CH₂OCH₂CH₂—, CH₃CH₂0CH₂CH₂OCH₂CH₂—, C₄H₉OCH₂CH₂OCH₂CH₂—,ethylthiopropyl, octylthiopropyl, dodecyloxypropyl, 2-hydroxyethyl,2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, —CH₂CH₂—N—H—C₄H₉,—CH₂CH₂CH₂NH—C₈H₁₇ and —CH₂CH₂CH₂—N(CH₃)—CH₂CH(C₂H₅)C₄H₉,

E₆, E₇, E₈, E₁₁ and E₁₂ can be the following C₅-C₁₂cycloalkyl radicals:cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclodecyl. In thecase of E₆, the radical can also be substituted by —OH.

E₇, E₈ and E₁₁ can be the following alkenyl radicals: allyl, methallyl,2-n-hexenyl or 4-n-octenyl.

When E₆ is alkenyl, it can have the same meaning as E₇, E₈ and E₁₁ asalkenyl radicals, but it can also be —CH═CH₂, n-undec-10-enyl orn-octadec-9-enyl, and it is also possible for the radical E₆ to besubstituted by —OH.

E₇ and E₈ can be the following C₇-C₁₅aralkyl radicals: benzyl,α-phenethyl, 2-phenethyl or 4-tert-butylbenzyl.

When E₁₁, E₁₃ or E₁₂ are aralkyl, they can, independently of oneanother, have the same meaning as E₇ or E₈.

Independently of one another, E₇, E₈ and E₁₁ can be the following C₆-C₁₄aryl radicals: phenyl, α-naphthyl or β-naphthyl.

When E₇ and E₈ are C₁-C₃ hydroxyalkyl, they can be the followingradicals: hydroxymethyl, 2-hydroxyethyl or 2-hydroxypropyl.

As C₂-C₈ alkylene, E₉ and E₁₄ can be the following radicals: ethylene,propylene, butylene, hexylene or octylene.

As alkylene, E₁₀ can be the same radicals, but can, in addition, also behigher-molecular groups such as decylene or dodecylene.

When E₉ is a C₄-C₈alkenylene radical, the following is an example of asuitable group: butenylene.

In the case of E₉ and E₁₄, suitable straight or branched chainC₄-C₁₀alkylene groups which are interrupted by —O— are the followinggroups: —CH₂CH₂OCH₂CH₂—,—CH(CH₃)—CH₂—O—CH₂—CH(CH₃)——CH₂CH₂0CH₂CH20CH₂CH₂— and—CH₂CH₂OCH₂CH₂OCH₂CH₂OCH₂CH₂—

When E₁₄ is a cycloalkylene radical, the following groups are embraced:1,3-cyclohexylene and 1,4-cyclohexylene.

When E₁₄ is arylene, this can be, specifically, the following groups:1,3-phenylene or 1,4-phenylene.

As C₂-C,₂-alkylene, Z is a straight or branched chain. It is forexample: ethylene, propylene, tetramethylene, hexamethylene,octanethylene, dodecamethylene, 1,1-ethylidene, 2,2-propylidene,2,2-amylidene or 2-ethylhexamethylene. C2-C₆-alkylene groups arepreferred.

When Z is C₄-C₁₂-alkylene which is interrupted by oxygen, it is forexample: —CH₂—CH₂—O—CH—₂—CH₂—, —CH₂—CH₂—O—CH₂—CH₂—CH₂,CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂ or —CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂—,and, when alkylene is interrupted by nitrogen, a group —N(E₁₆)— ismeant, where E₁₆ is as defined in the foregoing, for example—CH₂—CH₂—NH—CH₂—CH₂—CH₂—CH₂, —CH₂—CH₂—CH₂—NH—(CH₂)₈— or—CH₂CH₂—CH₂—N(CH₃—CH₂—CH(C₂H₅)(CH₂)₄—.

As C₃-C₁₂-alkylene substituted by a hydroxyl group, Z is2-hydroxytetramethylene, 2-hydroxyhexamethylene and, in particular,2-hydroxytrimethylene.

As cyclohexylene, Z is for example 1,4-cyclohexylene and, in particular,1,2-cyclohexylene.

As phenylene, Z is for example m-phenylene or p-phenylene.

m can be zero, 1, 2 or 3, but it is preferably 2.

p is preferably 1, but can also be zero if both X and Y are bound by wayof nitrogen.

As C₁-C₈-alkyl, E₁ is for example: methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, n-nexyl, n-heptyl,n-octyl, 2-ethylhexyl or tert-octyl. Tert-butyl is preferred.

As C₁-C₁₂-alkyl, E₁₆, E₁₇ and E₂₀ can have the same meaning as thatgiven in the foregoing for R₁, and can additionally be straight orbranched-chain nonyl, decyl, undecyl, or dodecyl.

When E₁₆ and E₁₇ are alkyl interrupted by oxygen atoms, the exampleswhich apply are the same as those described in the foregoing for Z.

Examples for E₁₆ and E₁₇ as aralkyl are: benzyl, α-methylbenzyl,1-phenylethyl, α,α-dimethylbenzyl or 1-phenylpropyl.

If Z is ethylene, E₁₆ and E₁₇ together can likewise form ethylene, whichis equivalent to a bridging over by way of a piperazine group.

When Y is a group —N(E₁₇)—, E₁₅ and E₁₇ together make up a group—CO—CH═CH—CO—, and thus form the substituent

on the group —X—(Z)_(p)—.

The preferred meaning of E₁₅ is, however, —CO—C(E₁₈)═CHE₁₄, E₁₈ and E₁₉are preferably methyl and especially hydrogen.

E₂ is —CH₂—CH₂—O—CO—C(G)═CH₂ and G is hydrogen or methyl.

The instant invention also pertains to a composition stabilized againstthermal, oxidative or light-induced degradation which comprises,

(a) an organic material subject to thermal, oxidative or light-induceddegradation, and

(b) an effective stabilizing amount of a compound of formula I, II, IIIor IV.

Preferably, the organic material is a natural, semi-synthetic orsynthetic polymer, especially a thermoplastic polymer.

Most preferably, the polymer is a polyolefin or polycarbonate,especially polyethylene or polypropylene; most especially polypropylene;or the polymer is a styrenic, ABS, a nylon, a polyester such aspoly(ethylene terephthalate) or poly(butylene terephthalate), apolyurethane, an acrylate, a rubber modified styrenic, poly(vinylchloride), poly(vinyl butaral), polyacetal (polyoxymethylene),poly(ethylene naphthalenedicarboxylate), or other blends or copolymerssuch as poly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETGor an ionomer as described on page 29.

In another preferred embodiment of the instant invention, the organicmaterial is a resin selected from the group consisting of a thermosetacrylic melamine resin, an acrylic urethane resin, an epoxy carboxyresin, a silane modified acrylic melamine, an acrylic resin withcarbamate pendant groups crosslinked with melamine or an acrylic polyolresin crosslinked with melamine containing carbamate groups.

Most preferably, the resin is a thermoset acrylic melamine resin or anacrylic urethane resin.

In yet another preferred embodiment of the instant invention, theorganic material is a recording material.

The recording materials according to the invention are suitable forpressure-sensitive copying systems, photocopying systems usingmicrocapsules, heat-sensitive copying systems, photographic materialsand ink jet printing.

The recording materials according to the invention are distinguished byan unexpected improvement in quality, especially with regard to thefastness to light.

The recording materials according to the invention have the constructionknown for the particular use. They consist of a customary carrier, forexample, paper or plastic film, which has been coated with one or morelayers. Depending on the type of material, these layers contain theappropriate necessary components, in the case of photographic materials,for example, silver halide emulsions, dye couplers, dyes and the like.Material particularly suitable for ink jet printing has a layerparticularly absorptive for ink on a customary carrier. Uncoated papercan also be employed for ink jet printing. In this case the paper actsat the same time as the carrier material and as the ink-absorbent layer.Suitable material for ink jet printing is, for example, described inU.S. Pat. No. 5,073,448 which is incorporated herein by reference.

The recording material can also be transparent as, for example, in thecase of projection films.

The compounds of formula I, II, III or IV can be incorporated into thecarder material as early as the production of the latter, in theproduction of paper, for example, being added to the paper pulp. Asecond method of application is to spray the carder material with anaqueous solution of compounds of formula , II, III or IV or to add thecompounds to the coating composition.

Coating compositions intended for transparent recording materialssuitable for projection cannot contain any particles which scatterlight, such as pigments and fillers.

The dye-binding coating composition can contain a number of otheradditives, for example, antioxidants, light stabilizers (including alsoUV absorbers which do not fall under the scope of the UV absorbers ofthis invention), viscosity improvers, fluorescent brighteners, biocidesand/or antistatic agents.

The coating composition is usually prepared as follows: thewater-soluble components, for example, the binder, are dissolved inwater and stirred together, the solid components, for example, fillersand other additives already described, are dispersed in this aqueousmedium; and disperison is advantageously carried out by means ofdevices, for example, ultrasonic systems, turbine stirrers,homogenizers, colloid mills, bead mills, sand mills, high-speed stirrersand the like. The compounds of formula I, II, III or IV can be easilyincorporated into the coating composition.

The recording material according to this invention preferably contains 1to 5000 mg/m², in particular 50-1200 mg/m², of a compound of formula I.

As already mentioned, the recording materials according to the inventionembrace a wide field. The compounds of formula I, II, III or IV can, forexample, be employed in pressure-sensitive copying systems. They can beintroduced either into the paper in order to protect themicroencapsulated dye precursors there from light, or into the binder ofthe developer layer in order to protect the dyes formed there.

Photocopying systems using light-sensitive microcapsules which aredeveloped by means of pressure are described in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463; 4,551,407;4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A 162,664; EP-A164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129. In all thesesystems, the compounds can be put into the dye-receiving layer. Thecompounds can, however, also be put into the donor layer in order toprotect the color formers from light.

Photographic materials which can be stabilized are photographic dyes andlayers containing such dyes or precursors thereof, for example,photographic paper and films. Suitable materials are, for example,described in U.S. Pat. No. 5,364,749 which is incorporated herein byreference. The compounds of formula I, II, III or IV act here as a UVfilter against electrostatic flashes. In color photographic materials,couplers and dyes are also protected against photochemicaldecomposition.

The instant compounds can be used for all types of color photographicmaterials. For example, they can be employed for color paper, colorreversal paper, direct-positive color material, color negative film,color positive film, color reversal film and the like. They arepreferably used inter alia for photographic color material whichcontains a reversal substrate or form positives.

Color-photographic recording materials usually contain, on a support, ablue-sensitive and/or a green-sensitive and/or a red-sensitive silverhalide emulsion layer and, if desired, a protection layer, with theinstant compounds being, preferably, either in the green-sensitive orthe red-sensitive layer or in a layer between the green-sensitive andthe red-sensitive layer or in a layer on top of the silver halideemulsion layers.

The compounds of formula I, II, III or IV can also be employed inrecording materials based on the principles of photopolymerization,photoplasticization or the rupture of microcapsules, or in cases whereheat-sensitive and light-sensitive diazonium salts, leuko dyes having anoxidizing agent or dye lactones having Lewis acids are used.

Furthermore, the instant compounds can be employed in recordingmaterials for dye diffusion transfer printing, thermal wax transferprinting and non-matrix printing and for use with electrostatic,electrographic, electrophoretic, magnetographic andlaser-electrophotographic printers and pen-plotters. Of the above,recording materials for dye diffusion transfer printing are preferred,for example, as described in EP-A 507,734.

The instant compounds can also be employed in inks, preferably for inkjet printing, for example, as described in U.S. Pat. No. 5,098,477 whichis incorporated herein by reference.

The compounds of this invention exhibit superior hydrolytic stability,handling and storage stability as well as good resistance toextractability when present in a stabilized composition.

The methodology to make the instant compounds is described in the priorart. The intermediates needed to make the instant compounds are largelyitems of commerce.

Preferred compounds are those in which one of X and Y is —O—; andparticularly those in which both X and Y are —O—.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, Vlb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-croordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylenel styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,especially polymers of halogen-containing vinyl compounds, for examplepolyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,polyvinylidene fluoride, as well as copolymers thereof such as vinylchloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/ butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer, polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terninated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from-diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

33. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

34. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.05 to about 3%, and especially 0.05to about 1%. However, some high performance films or in UV absorbinglayers of laminates such as those produced by coextrusion may containfrom 5-15% by weight of the instant compounds. Concentrations of 5-10%by weight are typical in certain coextrusion applications.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain from about 0.01 to about 5%, preferably from about 0.025 toabout 2%, and especially from about 0.1 to about 1% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

1. Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,&dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5 di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2′-thio-bis-(6-tert-butyl-4-methylphenol)

2,2′-thio-bis-(4-octylphenol)

4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

4,4′-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2′-methylene-bis-[4-methy-6-(α-methylcyclohexyl)-phenol]

2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2′-methylene-bis-(-nonyl-4-methylphenol)

2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2′-methylene-bis-(4,-di-tert-butylphenol)

2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4′-methylene-bis-(2,6-di-tert-butylphenol)

4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1 -bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)-6tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methvlphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-tethylenediamine

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

1.10 Diarylamines, for example,

diphenylamine, N-phenyl-l-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,

4,4′-di-tert-octyldiphenylamine, reaction product of N-phenylbenzylamineand

2,4,4-trimethylpentene, reaction product of diphenylamine and2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and2,4,4-trimethylpentene.

2. UV Absorbers and Light Stabilizers

2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the 5′-methyl-,3′,5′-di-tert-butyl-, 5′-tert-butyl-, 5′-(1,1,3,3-tetramethylbutyl)-,5-chloro-3′,5′-di-tert-butyl-, 5-chloro-3′-tert-butyl-5′-methyl-,3′-sec-butyl-5′-tert-butyl-, 4′-octoxy, 3′,5′-di-tert-amyl-,3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3′-dodecyl-5′-methyl-, and 3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-,and dodecylated-5′-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2′,4′-trihydroxy-and 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tertbutylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetrarmethylpiperidin-4-yl) sebacate.

2.7. Oxalic acid diamides, for example, 4,4′-di-octyloxy-oxanilide,2,2′-di-octyloxy-5,5′di-tert-butyl-oxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy4(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N′-diphenyloxalic acid diamide,N-salicylal-N′-salicyloylhydrazine, N,N′-bis-salicyloylhydrazine,N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino- 1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butyl-6methylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4′-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-dtetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alphaheptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

13. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. Nos. 4,325,863, 4,338,244 or 5,175,312, or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxylphenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)-benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The co-stabilizers, with the exception of the benzofuranones listedunder 13, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

Further preferred compositions comprise, in addition to components (a)and (b) further additives, in particular phenolic antioxidants, lightstabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 ofthe list), sterically hindered amines (item 2.6 of the list), phosphitesand phosphonites (item 4 of the list), UV absorbers (item 2 of the list)and peroxide-destroying compounds (item 5 of the list).

Additional additives (stabilizers) which are, also particularlypreferred are benzofuran-2-ones, such as described, for example, in U.S.Pat. Nos. 4,325,863, 4,338,244 or 5,175,312.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol, 2,2′-ethylidene-bis(4,6di-tert-butylphenol),1,3,5-tris(2,6-dimethyl4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl4hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl- 1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2] heneicosane,polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazineand 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4′-hexanethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin4-yl)-amino-s-triazin-2-yl]-1,10diamnino-4,7-diazadecane, mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin 4yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],and2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidintyl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecanedi-(1ctyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-([6-tert-octylamino-s-triazin-2,4diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylaminol-s-triazine.

The instant composition can additionally contain another UV absorberselected from the group consisting of the benzotriazoles, s-triazines,the oxanilides, the hydroxybenzophenones, benzoates and theα-cyanoacrylates.

Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from thegroup consisting of

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;

5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; and

2-(2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl }-2H-benzotriazole.

Preferably, the other tris-aryl-s-triazine is selected from the groupconsisting of

2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;

2,4bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine;and

2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-triazine.

The alkyd resin lacquers which can be stabilized against the action oflight and moisture in accordance with the instant invention are theconventional stoving lacquers which are used in particular for coatingautomobiles (automobile finishing lacquers), for example lacquers basedon alkyd/melamine resins and alkyd/acrylic/melamine resins (see H.Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages 99-123). Othercrosslinking agents include glycouril resins, blocked isocyanates orepoxy resins.

The lacquers stabilized in accordance with the invention are suitableboth for metal finish coatings and solid shade finishes, especially inthe case of retouching finishes, as well as various coil coatingapplications. The lacquers stabilized in accordance with the inventionare preferably applied in the conventional manner by two methods, eitherby the single-coat method or by the two-coat method. In the lattermethod, the pigment-containing base coat is applied first and then acovering coat of clear lacquer over it.

It is also to be noted that the compounds of the present invention areapplicable for use in non-acid catalyzed thermoset resins such as epoxy,epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionallymodified with silicon, isocyanates or iso cyanurates. The epoxy andepoxy-polyester resins are crosslinked with conventional cross-linkerssuch as acids, acid anhydrides, amines and the like. Correspondingly,the epoxide may be utilized as the crosslinking agent for variousacrylic or polyester resin systems that have been modified by thepresence of reactive groups on the backbone structure.

When used in two-coat finishes, the compounds of the instant inventioncan be incorporated in the clear coat or both in the clear coat and inthe pigmented base coat.

When water-soluble, water miscible or water dispersible coating aredesired ammonium salts of acid groups present in the resin are formed.Powder coating composition can be prepared by reacting glycidylmethacrylate with selected alcohol components.

The instant benzotriazoles are made by conventional methods forpreparing such compounds. The usual procedure involves the diazotizationof a substituted o-nitroaniline followed by coupling the resultantdiazonium salt with a substituted phenol and reduction of the azobenzeneintermediate to the corresponding desired benzotriazole. The startingmaterials for these benzotriazoles are largely items of commerce or canbe prepared by normal methods of organic synthesis.

While the instant benzotriazoles with their enhanced durability areparticularly suited for automotive coating applications, it iscontemplated that they will also be espeically useful in otherapplications where their enhanced durability is required such as insolar films and the like.

The following examples are for illustrative purposes only and are not tobe construed to limit the scope of the instant invention in any mannerwhatsoever.

EXAMPLE 15-Trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

a. Diazotization of 4-amino-3-nitro-benzotrifluoride

To a 500 ml 3-necked flask, equipped with a mechanical stirrer, areadded 41.2 g of 4-amino-3-nitro-benzotrifluoride, 52 ml of concentratedhydrochloride acid and 100 ml of distilled water. The stirred solutionis cooled to 5° C. and 17.3 g of sodium nitrite dissolved in 50 ml ofwater are added. The solution is stirred at 0 to 5° C. for two hours,then filtered and stored at −10° C.

b. Monoazo Adduct

To a 1000 ml flask, fitted with a mechanical stirr, are added 40 g ofsodium hydroxide dissolved in 200 ml of methanol and 32.4 g of2-α-cumyl-4-tert-octylphenol in 50 ml of xylene. The solution is cooledto 5° C. and the diazo solution of 4-amino-nitrobenzotrifluorideprepared in part a. is added at 0 to 5° C. over a two-hour period. Then100 ml of xylene are added and the organic layer is washed with water,aqueous hydrochloride acid, water, aqueous sodium bicarbonate solutionand finally water. The solvent is removed under reduced pressure and theresidue is purified by chromatography (silica gel, heptane:ethyl acetate95:5) to yield 42.1 g of the adduct product as a dark red paste.

c. Reduction of the Monoazo Adduct

A 1000 ml flask is charged with 20 g of sodium hydroxide, 40 ml ofwater, 42.1 g of the monoazo adduct prepared in part b. and 400 ml ofethanol. The mixture is warmed to 80° C. and 27 g of formamidinesulfinic acid is added in portions with stirrng. After 1.5 hours, thesolution is cooled to room temperature and 100 ml of water are added.The pH is adjusted to pH 7 with concentrated hydrochloric acid. Theethanol is removed under vacuum and the water layer is extracted withmethylene chloride. The solvent is then evaporated in vacuo and theresidue is purified by chromatography (silica gel, heptane:tolunen 9:1)and crystallized from ethanol. The title compound is obtained in a yieldof 5.6 g as a pale yellow solid melting at 119-121° C.

EXAMPLE 25-Fluoro-2-(2-hydroxy-3α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The title compound is prepared according to the general procedure ofExample 1 using 31.2 g of 4-fluoro-2-nitroaniline. In part c of theprocedure, an additional 9 g of formamidine sulfinic acid is required tocomplete the reduction. Purification of the crude product on silica gel(heptane:toluene, 1:1) yields 4.5 g of the title compound as a off-whitesolid. Further purification by recrystallization fromacetonitrile:toluene provides 1.1 g of the title compound melting at93-96° C.

EXAMPLE 35-Chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The general procedure of Example 1 parts a and b is followed to preparethe monoazo intermediate of making the title compound from 339.3 g of4-chloro-2-nitroaniline. The crude product is purified byrecrystallization from methanol to yield 70.9 g of deep red monoazoadduct.

Reduction of the Monoazo Adduct

A mixture of 11.8 g of sodium hydroxide and 138 g of 2-butanol is heatedto 95° C. A solution of 60.1 g of the above monoazo adduct and 1.3 g of2,3-dichloro-1,4-naphthoquinone in 90 g of 2-butanol is added over a 90minute period with stirring. The reaction mixture is heated to removethe 2-butanone byproduct with additional 2-butanol added to replace thedistillate. The reaction mixture is cooled to 85° C., washed with 2.5 Nsulfuric acid and brine and then concentrated. The residue isrecrystallized from methanol:xylene to yield 45.6 g of the titlecompound as a light yellow solid melting at 104-105° C.

EXAMPLE 45-Phenylthio-2-(2-hydroxy-3-α-cumyl-5-tert-otylphenyl)-2H-benzotriazole

To a stirred mixture of 75 g of5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole and105 g of N-methylpyrrolidone heated at 90° C. is added first 44.3 g of45% aqueous potassium hydroxide solution over a 15-minute period then20.4 g of thiophenol over another 15 minutes. The reaction mixture isthen heated at 170-175° C. for four hours with water being removed bydistillation. After cooling to 100° C., xylene and water are added andthe resultant mixture is made acidic with 15% aqueous hydrogen chloridesolution. The organic layer is separated and washed with water and thenconcentrated. The crude product residue is recrystallized from methanolto yield 82 g of the title compound as a pale yellow solid melting at124-125° C.

EXAMPLE 55-Benzenesulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

A 1000 mL flask is charged with 75.2 g of5-phenylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 4, 102 g of xylene, 0.9 g of sodium tungstatedihydrate and 18.4 g of formic acid. The mixture is heated to 50° C. Tothis stirred mixture is slowly added 36.3 g of 50% hydrogen peroxide sothat the temperature does not exceed 85° C. Additional xylene and waterare then added. The organic layer is separated, washed with aqueoussodium sulfite, then twice with water and concentrated. The crudeproduct residue is recrystallized from methanol to yield 75.2 g of thetitle compound as a light yellow solid melting at 170-171° C.

EXAMPLE 65-Nonylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

Using the procedure of Example 4 with 30 g of5-chloro2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole and17.6 g of nonyl mercaptan, the title compound is prepared.

EXAMPLE 75-Nonylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

5-Nonylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 6, is oxidized to the sulfone without purificationof the thio intermediate using 8.7 g of formic acid, 0.7 g of sodiumtungstate dihydrate and 17.6 g of 50% hydrogen peroxide to yield thetitle compound as a yellow resin exhibiting a molecular ion of m/e 631.This process is described in detail in copending application Ser. No.09/234,879.

EXAMPLE 85-Chloro-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

The general procedure of Example 1 parts a and b are used to prepare themonoazo intermediate for the title compound from 4-chloro-2-nitroanilineand 2-phenyl4-tert-octylphenol. The crude product is purified byrecystallization from methanol to yield a deep red monoazo adduct.

The title compound is prepared according to the reduction procedure ofExample 3 from 65 g of the monoazo adduct prepared above, 19.9 g ofsodium hydroxide and 2.4 g of 2,3-dichloro-1,4-naphthoquinone. The crudeproduct is purified by chromatography on silica gel (hexane:ethylacetate, 5:1) yielding a fraction which is predominantly the titlecompound exhibiting a molecular ion of m/e 433.

EXAMPLE 95-Phenylthio-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

The title compound is prepared according to the procedure of Example 4from 20 g of the compound of Example 8, 20.4 g of 45% aqueous potassiumhydroxide, 10.3 g of thiophenol and 100 g of N-methylpyrrolidone. Thetitle compound is an oil purified by chromatography on silica gel usingtoluene as eluent.

EXAMPLE 105-Benzenesulfonyl-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

The title compound is prepared according to the procedure of Example 5from 20 g of the thio compound of Example 9, 6.4 g of formic acid, 15.0g of 50% hydrogen peroxide and 0.6 g of sodium tungstate dihydrate.Recrystallization of 2.5 g of crude material from xylene/methanol yields2.0 g of the purified title compound as a light yellow powder melting at204-206° C.

EXAMPLE 11 Mixture of5-Chloro-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole (alkyl beingindependently C₄, C₈, C₁₂ and C₁₆)

A mixture of 65.4 g of5-chloro-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole, 45 mL ofdodecene and 13 mL of methane sulfonic acid is heated to 170° C. undernitrogen. An additional 135 mL of dodecene is added over a 4.5 hourperiod. The reaction mixture is allowed to cool to 100° C. and thenquenched with 400 g of crushed ice and extracted thrice with ethylacetate. The organic layers are combined, washed with water, aqueoussodium bicarbonate, water again and brine, dried over anhydrousmagnesium sulfate and finally concentrated. The polymeric residue isremoved by bulb to bulb distillation under vacuum at 0.2 mm and up to210° C. Unreacted starting material is then removed by distillation (at0.01 mm,160° C.) to give 45 g of the title mixture as a yellow oil.

EXAMPLE 12 Mixture of5-Phenylthio-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole (alkylbeing independently C₄, C₈, C₁₂ and C₁₆)

The title mixture is prepared according to the procedure of Example 4using 40 g the mixture of Example 11, 11.2 g of potassium hydroxide and12.3 mL of thiophenol.

EXAMPLE 13 Mixture of5-Benzenesulfonyl-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole(alkyl being independently C₄, C₈, C₁₂ and C₁₆)

A mixture of the crude product of Example 12, 350 mL of isopropanol,14.7 mL of formic acid and 1.8 mL of concentrated sulfuric acid areheated to reflux and 30 mL of 50% hydrogen peroxide is added dropwiseover a two-hour period. After an additional three hours at reflux, thereaction mixture is cooled and 10% aqueous sodium sulfite and aqueoussodium bicarbonate are added. The isopropanol is evaporated and theresidue is extracted with methylene chloride. The organic layer iswashed with water and then dried over anhydrous magnesium sulfate. Thesolution is concentrated to leave 45 g of crude product as a viscousprange oil. Some 30 g of this crude product is purified bychromatography on silica gel (heptane:ethyl acetate, 4:1) to yield 28.9g of the title mixture as a yellow oil.

EXAMPLE 145-Diphenylphosphinyl-2-(2-hydroxy-3,5-tert-butylphenyl)-2H-benzotriazole

To a flame-dried 500 mL three-necked round-bottomed flask equipped witha condenser, magnetic stirrer and thermometer are charged 100 mL ofdimethyl sulfoxide, 7.41 g (0.066 mol) of potassium tert-butoxide and11.17 g (0.060 mol) of diphenylphosphine via a syringe. A slurry of10.56 g (0.030 mol) of 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole in 50 mL of dimethyl sulfoxideis added all at once to the red mixture. The resultant brown solution isstirred at 135° C. for 3.5 hours and then cooled to room temperature.The mixture is quenched with a portion of saturated ammonium chloridesolution and ethyl acetate is then added. The organic layer is separatedand washed thrice with water, once with brine and then dried overanhydrous magnesium sulfate. To the solution is added 50% hydrogenperoxide resulting in an exotherm. The mixture is allowed to sit for 30minutes, then washed once with 10% sodium metabisulfite solution thricewith saturated sodium bicarbonate solution once with brine and finallydried over anhydrous magnesium sulfate. The mixture is filtered with aplug of silica gel and the solvent is removed under reduced pressure toyield 8.0 g of a crude yellow solid. The crude product is treated withmedium pressure chromatography using heptane:ethyl acetate, 1:1 toafford 4.2 g (27% yield) of the title compound as a yellow solid meltingat 98-100° C.

EXAMPLE 155-Diphenylphosphinyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

Following the procedure of Example 14, the title compound is preparedwhen5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole isused as the starting benzotriazole intermediate.

EXAMPLES 16-26

Following the general procedure of Example 1, the following additional2H-benzotriaazoles of formula I are prepared.

Example G₂ E₁ E₂ 16 CF₃ phenyl tert-octyl 17 CF₃ α-cumyl tert-butyl 18CN α-cumyl tert-octyl 19 CN α-cumyl nonyl 20 CN α-cumyl tert-butyl 21COOCH₃ α-cumyl dodecyl 22 F phenyl tert-octyl 23 CF₃ α-cumyl nonyl 24CF₃ α-cumyl dodecyl 25 CON(Bu)₂ α-cumyl tert-octyl 26 COOCH₃ phenyltert-octyl

EXAMPLE 275-Octylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

Using the procedure of Example 6 with5-chloro-2-(2-hydroxy-3-α-cumyl-5-tertoctylphenyl)-2H-benzotriazole andoctyl mercaptan, the tidtle compound is prepared.

EXAMPLE 285-Octylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

5-Octylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 27, is oxidized to the sulfone without purificationof the thio intermediate using the general method of Example 7. A yellowresinous liquid is obtained whose structure is consistent as measured by¹HNMR

EXAMPLE 295-Carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

a. Esterification of 4-amino-3-nitrobenzoic Acid

To a 2 L 3-necked flask fitted with a mechanical stirrer are added 700mL of methanol, 20 g of xylene, 14 g concentrated sulfuric acid and 100g of 4-amino-3-nitrobenzoic acid. The solution is heated to reflux for33 hours. The mixture is cooled to 35° C. and neutralized to pH 7.8.Water (1 L) is added, the solid collected and washed with 500 ml to giveafter drying overnight 100.9 g of methyl 4-amino-3-nitrobenzoate.

b. Diazotization of methyl 4-amino-3-nitrobenzoate

To a 1 L 3-necked flask fitted with a mechanical stirrer is added 177 gof 96% sulfuric acid and then slowly over 90 minutes 11 g of sodiumnitrite. The mixture is warmed to 30° C. to initiate the reaction. Thetemperature is kept below 70° C. The mixture is then cooled to 15° C.and 30 g of methyl 4-amino-3-nitrobenzoate is added over two hourskeeping the temperature between 15-20° C. The mixture is cooled to 0° c.and 200 g of ice is added to make the solution suitable for the couplingreaction to form a monoazo compound.

c. Monoazo Adduct

To a 2 L 3-necked flask fitted with a mechanical stirrer and additionfunnel are added 52 g of 2-α-cumyl-4-tert-octylphenol, 20 g of water,315 g of methanol, 7 g of xylene and 150 g of sodium hydroxide. Themixture is cooled to −5° C. and the diazonium salt solution prepared isstep b. is added over a two hour period with cooling to keep thetemperature below 3° C. After the diazonium salt solution is added, thepH is adjusted to 6.5-7.0. The mixture is poured into 500 mL of xyleneand washed thrice with 500 mL of water at 60° C. The xylene is removedby distillation to give 186 g of the monoazo adduct containing residualxylene.

d. Reduction of the Monoazo Adduct

To a 500 mL flask fitted with a mechanical stirrer is added the 186 g ofmonoadduct prepared in step c., 125 g of 2-butanol and 1.7 g of2,3-dichloro-1,4-naphthoquinone. The mixture is heated to 90° C. and theresulting solution is then charged to the addition funnel on a separateflask. In said second flask are added 175 g of 2-butanol and 18.6 g ofsodium hydroxide, The flask is heated to 95° C. and the monoazo solutionis added over two hours while distilling off methyl ethyl ketone and2-butanol. 2-Butanol (100 g) is added and an azeotrope is distilled off.The mixture is then cooled and 300 g of xylene and 200 mL of water areadded. The pH is adjusted to 7-7.5 with 20% sulfuric acid. At 60° C.,the aqueous phase is separated and the organic phase washed twice with200 mL of water. The xylene is removed by distillation and the residueformed is crystallized from methanol to give 8.8 g of the title compoundmelting at 141-143° C.

EXAMPLE 305-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl]-2H-benzotriazole

a. Saponification of5-Carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

To a 250 mL 3-necked flask equipped with a mechanical stirrer,thermometer, condenser and nitrogen inlet is added 1.8 g of potassiumhydroxide and 40 mL of methanol. The mixture is warmed to 40° C. todissolve the potassium hydroxide. To this solution is added 2.7 g of5-carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 36, in 40 mL of methanol. The reaction mixture isrefluxed for six hours. The mixture is then cooled and acidified withhydrochloric acid. Ether and ethyl acetate are added, and the organiclayer is separated and dried over anhydrous sodium sulfate. After vacuumstripping of the solvent, 2.5 g of5-carboxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole isisolated.

b.5-Chlorocarbonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The 2.5 g of5-carboxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in step a, are placed in a 250 mL flask equipped with astirrer, thermometer, reflux condenser, Dean-Stark trap and nitrogeninlet Toluene (100 mL) is added and the mixture is reflux to remove anytraces of water. The mixture is then cooled and 0.76 g of oxalylchloride in 15 mL of toluene is added. The reaction mixture is heatedslowly to 60° C. and held at 60-65° C. for eight hours till all thehydrogen chloride is expelled to give the acid chloride title compound.

c.5-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl]-2H-benzotriazole

To a 500 mL flask equipped with a mechanical stirrer, drying tube,thermometer and dropping funnel are added 0.8 g of di-n-butylamine, 6 mLof pyridine and 25 mL of toluene. The mixture is cooled to 0° C. and theacid chloride solution prepared in step b. is placed in the droppingfunnel and added to the reaction mixture over a 30-minute period at −5°C. to −10° C. The reaction mixture is stirred at that temperature for1.5 hours and then held at ambient temperature overnight. The mixturewas filtered and then vacuum stripped to give 3.0 g of crude solids. Thesolid product is chromatographed to provide 1.2 g of the title compoundas a tan solid melting at 131-133° C. The structure is confirmed by nmrand mass spectrometry m/z 596.

EXAMPLE 315-Trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole

The tide compound is prepared according to general procedure of Example1 the diazo compound of 4-amino-3-nitrobenzotrifluoride and4-tert-octylphenol, and which is purified by chromatography on silicagel. Recrystallization of the product from either heptane or methanolyields the title compound as a near white solid melting at 80-81° C.

EXAMPLE 325-n-Butylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

5-Chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)2H-benzotriazole (21.2 g,0.06 mol), n-butyl mercaptan (7.2 g, 0.08 mol), potassium hydroxide(6.7.1 g, 0.12 mol) and N-methylpyrrolidone (50 g, 0.5 mol) are chargedto a reactor and heated to 150° C. The reaction mass is held at 150° C.for 4.5 hours at which time it then cooled to ambient temperature. Amixture of 15 g of concentrated hydrochloric acid and 70 g of ice arethen added to the reactor. The solids are filtered off and washed withwater. Thirty gram of crude, wet, yellow crystals are obtained as thetitle compound. This product can be used “as is” in procedure of Example33.

EXAMPLE 33

5-n-Butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

The product as prepared in Example 32 (39.5 g, 0.1 mol), formic acid (10g, 0.2 mol), sodium tungstate (0.33 g, 0.001 mol) and xylenes (100 mL)are charged to a reactor and heated to 50° C. Hydrogen peroxide (27.2 g,0.4 mol) is charged dropwise over a one-hour period. The temperature israised to 75° C. and held there for four hours. The reaction is judgedcomplete using thin layer chromatography. The aqueous layer is split offand the organic phase is washed successively with 100 mL of sodiumsulfite solution, twice with sodium bicarbonate solution, with saturatedsodium chloride solution and then water. Xylene is stripped off and thecrude product is crystallized from ethanol and heptane. Thirty grams ofthe title compound are obtained as yellow needles melting at 156° C. Thestructure is verified by ¹Hnmr analysis.

EXAMPLE 342-[2-Hydroxy-3-(di-n-butylaminomethyl)-5-tert-octylphenyl]-2H-benzotriazole

2-[2-Hydroxy-5-tert-octylphenyl]-2H-benzotriole (30 g, 0.092 mol),paraformaldehyde (3 g, 0.0955 mol) and di-n-butylamine (24.9 g, 0.191mol) are charged to a pressure reaction at ambient temperature. Thereactor is sealed and the temperature raised to 160° C. The reactionmass is held at 160° C. for four hours and then discharged The reactoris rinsed with toluene. The toluene, amine and water are stripped byrotary evaporation. The crude product is prepared in a 96% yield (40 g).This product is chromatographed on silica gel using a heptane/ethylacetate gradient as eluent to remove a trace of unreacted startingbenzotriazole intermediate. The title compound is a yellow oil whosestructure is confirmed by ¹Hnmr.

EXAMPLE 35Methylene-[2-(4-tert-octyl-6-2H-benzotriazol-2-yl)phenol]{2′-[4-tert-octyl-6-(5-trifluoromethyl)-2H-benzotriazol-2-yl}phenol}

Trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (10 g,0.025 mol, as prepared in Example 31), sodium methoxide (1.49 g, 0.026mol) and xylenes (20 g, 0.187 mol) are added to a reaction flask whichis then heated to 160° C. The compound prepared in Example 34 (11.75 g,0.0253 mol) dissolved in 11.8 g of xylenes is dripped into the reactionmass over a one-hour period. At the end of the addition, the reactionmass is heated to 205° C. while distilling off xylene, methanol anddi-n-butylamine. After one hour at 205° C, the reaction mass issubjected to a 26″ Hg vacuum for three hours. After the vacuum isreleased, the reaction mass is cooled to 100° C. and 100 g of heptane ischarged. The solution is then washed with 50 g of 10% aqueoushydrochloric acid followed by 50 g of water. The heptane is dried andthe product is crystallized and isolated by filtration. After washingthe filter cake with heptane, the product is dried to constant weight invacuo. The title compound is obtained as a solid (16 g, 87% yield)melting at 163-166° C.

Analysis

Mass spectrometry: 727 (M+H);

¹Hnmr (CDCl₃): δ0.71 (s, 9H), 0.72 (s, 9H), 1.40 (s, 6H), 1.41 (s, 6H)1.74 (s, 2H), 1.75 (s, 2H), 4.31 (s, 2H), 7.38 (d, 1H), 7.42 (d, 1H),7.48 (complex, 2H), 7.68 (dd, 1H), 7.95 (complex, 2H), 8.08 (d, 1H),8.29-8.33 (3d, 3H), 11.54 (s, 1H)

EXAMPLE 365-n-Butylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

5-Chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole(38.1 g, 0.08 mol), n-butyl mercaptan (9 g, 0.10 mol), potassiumhydroxide (10.1 g, 0.18 mol) and N-methylpyrrolidone (99 g, 1.0 mol) arecharged to a reactor and heated to 170° C. The reaction mass is held at170° C. with vigorous stirring for five hours. The reaction is judged ascomplete using thin layer chromatogrphy. The temperature is reduced to5° C. and 100 mL of aqueous 2N hydrochloric acid are then added to thereactor. The liquid is decanted and the solids are dissolved in ethylacetate. The organic layer is washed with aqueous 2N hydrochloric acidfollowed by water. The ethyl acetate is stripped off and the product iscrystallized from ethanol and toluene. The title compound is obtained asa yellow crystalline product in 83% yield. The structure is verified by¹Hnmr.

EXAMPLE 375-n-Butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The product prepared in Example 36 (34.2 g, 0.065 mol), formic acid (6.8g, 0.13 mol), sodium tungstate (0.21 g, 0.00065 mol) and xylenes (100mL) are charged to a reactor and heated to 50° C. Hydrogen peroxide(17.7 g, 0.26 mol) is charged dropwise over a one-hour period. After theaddition is complete, the reaction mass is held at 50° C. for 3.5 hours.The reaction is judged complete using thin layer chromatography. Thereaction mass is washed with 230 g of 14% sodium sulfite solution afterthe addition of 200 mL of xylene. The organic phase is washed with 200mL of saturated sodium bicarbonate solution, with 100 mL of saturatedsodium chloride solution and then with 200 mL of water. Xylene isstripped off to give a yellow oil which crystallized. The crude productis recrystallized from toluene/methanol to give a 55% yield of the titlecompound as a solid melting at 118° C. The structure is verified by¹Hnmr and mass spectrometry analysis.

EXAMPLE 38 Methyl3-(Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

The general procedure of Example 1, parts a and b, is followed toprepare the unisolated, solid, monoazo intermediate of the titlecompound from 62.5 g of 4-amino-3-nitrobenzotrifluoride(=4-trifluoromethyl-o-nitroaniline).

The monoazo intermediate (84 g, 0.19 mol), xylenes (116 g, 1.08 mol),diethylamine (100 g, 1.4 mol) and 5% palladium on charcoal (0.5 g, 50%assay) are charged to a reactor. Hydrazine (27.4 g, 0.56 mol) is drippedin over a two-hour period at a temperature range of 15-45° C. After theaddition is complete, the temperature is raised to 80° C. and held therefor three hours. The reaction is judged complete by thin layerchromatography. The catalyst is removed by filtration and the solventremoved in vacuo to yield 36 grams of the product. Afterrecrystallization from methanol, the title compound is obtained as lightyellow needles melting at 105-107° C.

Analysis

Mass spectrometry: 422 (M+H);

¹Hnmr (CDCl₃): δ1.51 (s, 9H), 2.71 (t, 2H), 3.02 (t, 2H), 3.71 (s, 3H),7.26 (d, 1H), 7.69 (dd, 1H), 8.07 (d, 1H), 8.17 (d, 1H), 11.55 (s, 1H)

EXAMPLE 393-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicAcid

The ester prepared in Example 38 (36 g, 0.088 mol), sodium hydroxide(16.4 g, 0.41 mol), N-methylpyrrolidone (12 g, 0.12 mol) and water (400g) are charged to a reactor and heated to 100° C. The solution isrefluxed for three hours after which the reaction mass is poured into500 g of 10% aqueous hydrochloric acid. The solids are removed byfiltration, washed with water and dried to a constant weight to give31.6 g of product. This material is recrystallized from toluene/acetoneto give the title compound as a light yellow solid melting at 166° C.

Analysis

Mass spectrometry: 406 (M−H);

¹Hnmr (CDCl₃): δ1.50 (s, 9H), 2.78 (t, 2H), 3.04 (t, 2H), 7.26 (d, 1H),7.65 (dd, 1H), 8.07 (d, 1H), 8.18 (d, 1H), 8.31 (d, 1H), 11.58 (s, 1H)

EXAMPLE 40 Isooctyl3-(Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

The acid prepared in Example 39 (8 g, 0.02 mol), EXXAL® 8 (isooctanolisomers, Exxon, 5 g, 0.038 mol), p-toluenesulfonic acid hydrate (0.5 g,0.0026 mol) and xylenes (100 mL) are charged to a reactor and refluxedfor six hours. TLC shows when the reaction is complete. The solvent isremoved and the resulting oil is chromatographed on silical gel. Thetitle compound is obtained in 99.5% yield as a light yellow oil.

Analysis

Mass spectrometry: 520 (M+H);

¹Hnmr (CDCl₃): δ0.73-1.79 (broad complex, 15H), 1.51 (s, 9H), 2.71 (t,2H), 3.02 (t, 2H), 4.10 (complex, 2H), 7.27 (d, 1H), 7.69 (dd, 1H), 8.08(d, 1H), 8.18 (d, 1H), 8.30 (s, 1H), 11.55 (s, 1H)

EXAMPLE 415-Trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole

Following the general procedure of Example 1, 62.5 g of4-amino-3-nitrobenzotrifluoride is used to make 42.5 g of the titlecompound which is obtained as yellow crystals melting at 100.5-101.5° C.

Analysis

¹Hnmr (CDCl₃): δ0.79 (s, 18H), 1.45 (s, 9H), 1.54 (s, 3H), 1.56 (s, 3H),1.82 (s, 2H), 2.12 (s, 2H), 7.44 (d, 1H), 7.66 (dd, 1H), 8.10 (d, 1H),8.30 (s, 1H), 8.32 (s, 1H), 11.55 (s, 1H)

EXAMPLE 425-Trifluoromethyl-2-(2-hydroxy-3-allyl-5-tert-octylphenyl)-2H-benzotriazole

The compound prepared in Example 31 (13.01 g, 0.033 mol), potassiumhydroxide (2.37 g, 0.036 mol) and ethanol (60 mL) are charged to areactor and stired at ambient temperature for two hours. Allyl bromide(4.84 g, 0.039 mol) and potassium iodide (0.34 g, 0.002 mol) are addedto the reaction mixture which is heated to 85° C. After holding at 85°C. for 4.5 hours, the solvent is removed and replaced with 100 mL ofheptane. The mixture is washed thrice with 40 mL of water. The solventis then removed to yield 14.2 g of the corresponding O-allyl ether as anoff-white solid.

Analysis

¹Hnmr (CDCl₃): δ0.78 (s, 9H), 1.41 (s, 6H), 1.77 (s, 2H), 4.60-4.65 (d,2H), 5.16-5.34 (m. 2H), 5.86-6.00 (m, 1H), 7.06-7.11 (d, 1H), 7.49-7.54(dd, 1H), 7.61-7.67 (m, 2H), 8.08-8.12 (d, 1H), 8.35 (s, 1H)

The O-allyl compound (14.2 g) as prepared above is charged to a reactorand heated to 190-195° C. and held at that temperature for five hours.Flash column chromatography with silica gel and ethyl acetate/heptanesolvent as eluent to give the title compound in 12.2 g yield as a yellowoil.

Analysis

Mass spectrometry: 432 (M+H);

¹Hnmr (CDCl₃): δ0.78 (s, 9H), 1.46 (s, 6H), 1.81 (s, 2H), 3.53-3.64 (d,2H), 5.06-5.20 (m, 2H), 6.02-6.18 (m, 1H), 7.29-7.34 (d, 1H), 7.66-7.72(dd, 1H), 8.05-8.12 (d, 1H), 8.29-8.35 (m, 2H), 11.17 (s, 1H)

EXAMPLE 432,2′-Methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol]

The compound prepared in Example 31 (7.0 g, 0.018 mol), paraformaldehyde(0.29 g, 0.0093 mol) and di-n-butylamine (2.43 g, 0.0186 mol) arecharged to a reaction and which is then sealed. The temperature isincreased to 160° C. and held there for four hours. The reaction mass iscooled to 110° C. at which time sodium methoxide (0.16 g, 0.0028 mol) isadded. The reaction mixture is then heated to 205° C. and held there forthree hours. The reaction mass is then cooled to 110° C. and 100 mL ofxylenes are added. The reaction mass is neutralized with 10% aqueoushydrochloric acid and the organic phase is twice washed with water.Xylene is then distilled off and replaced with heptane. After coolingthe heptane solution, yellow crystals separate out and are isolated byfiltration. After drying to constant weight, the title compound (5 g) isobtained as a solid melting at 178° C.

Analysis

¹Hnmr (CDCl₃): δ0.72 (s, 18H), 1.41 (s, 12H), 1.75 (s, 4H), 4.31 (s,2H), 7.42 (d, 2H), 7.68 (dd, 2H), 8.08 (d, 2H), 8.31 (d, 4H), 11.25 (s,2H)

EXAMPLE 44 2-(2-Hydroxy-5-tifluoromethylphenyl)-2H-benzotriazole

The title compound is prepared following the general procedure ofExample 1 starting with o-nitroaniline and 4-trifluoromethylphenol.Rigorous purification of the crude product on silica gel (heptane/ethylacetate 4: 1) followed by recrystallization from heptane yields thetitle compound as a yellow solid melting at 119-120° C. The structure isconfirmed by UV spectroscopy, mass spectrometry and ¹Hnmr.

Analysis

Mass spectrometry: m/z 279;

¹Hnmr (300 mHz, CDC1₃): δ7.31 (d, 1H), 7.54 (m, 2H), 7.61 (dd, 1H), 7.97(m, 2H), 8.74 (d, 1H), 11.75 (s, 1H)

UV Absorption (ethyl acetate) λ_(max) 328, ε20,500

EXAMPLE 455-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole

The title compound is prepared by reacting the ester compound of Example38 with lithium aluminum hydride according to the procedure of Example19 of U.S. Pat. No. 5,280,124. The title compound is obtained in 80%yield as a solid melting at 90-91° C.

EXAMPLE 465-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole

The title compound is prepared by the reaction of the compound ofExample 45 with methacryloyl chloride in the presence of triethylamninein toluene.

EXAMPLE 47-53

Following the general procedure of Example 45, the following compoundsof formula III are prepared where n is 1, m is 2 and E₅ is hydroxy.

Example G₁ G₂ E₁ E₃ 47 Cl F tert-butyl — 48 H CF₂ phenyl — 49 H CF₂allyl — 50 H CN α-cumyl — 51 H E₃SO α-cumyl butyl 52 H E₃SO₂ phenylphenyl 53 E₃SO₂ tert-octyl ethyl

EXAMPLE 545-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole

When using the general procedure of Example 1 the2-α-cumyl-4-tert-octylphenol is replaced by2-tert-butyl-4-(2-hydroxyethyl)phenol, the title compound is prepared.

EXAMPLE 555-Trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole

When using the general procedure of Example 1, the2-α-cumyl-4-tert-octylphenol is replaced by 4-(2-hydroxyethyl)phenol,the title compound is prepared.

EXAMPLE 565-Trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole

When using the general procedure of Example 1, the2-α-cumyl-4-tert-octylphenol is replaced by 2,4-di-α-cumylphenol, thetitle compound is prepared.

EXAMPLE 575-Trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

Using the general procedure of Example 1, 47.1 g of2,4di-tert-butylphenol is used to prepare 14.1 g of the title compoundas yellow needles melting at 131-133° C.

EXAMPLE 585-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-aminopropyl)phenyl]-2H-benzotriazole

The title compound is prepared by reacting the amide of the acidcompound of Example 39 with lithium aluminum hydride dissolved indiethyl ether according to the general procedure of Example 19 of U.S.Pat. No. 5,280,124.

EXAMPLE 595-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-methacryloylaminopropyl)phenyl]-2H-benzotriazole

The title compound is prepared by the reaction of the compound ofExample 58 with methacryloyl chloride in the presence of triethylaminein toluene.

EXAMPLE 60 Isomeric Mixture of3-[3-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-2-hydroxypropylMethacrylate and2-[3-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-3-hydroxypropylMethacrylate

Following the general procedure of Example 25 of U.S. Pat. No.5,280,124, the title compounds are prepared from the acid compound ofinstant Example 39 and glycidyl methacrylate in the presence oftetrabromoammonium bromide dissolved in toluene.

EXAMPLE 61-73

Following the general procedure of Example 45, the following compoundsof formula III are prepared where n is 1, m is 2 and E₅ is a mixture of—OCH₂CHOHCH₂OCOC(CH₃)═CH₂ and —OCH(CH₂OH)CH₂OCOC(CH₃)═CH₂.

Example G₁ G₂ E₁ E₃ G₃ 61 Cl F α-cumyl — — 62 H CF₃ phenyl — — 63 H CF₃hydrogen — — 64 H CF₃ cyclohexyl — — 65 H CF₃ tert-octyl — — 66 H CNα-cumyl — — 67 H F phenyl — — 68 Cl CN α-cumyl — — 69 H G₃CO- α-cumyl —methyl 70 H G₃CO- phenyl — phenyl 71 H E₃SO α-cumyl hexyl — 72 H E₃SO₂phenyl HOCH₂CH₂₋ — 73 H E₃SO₂ phenyl phenyl —

EXAMPLE 74 UV Absorption Data

The following table demonstrates the enhanced absorption of thecompounds of the instant invention for wavelengths above 350 nm. Whilethe λ max of the instant compounds is not always significantly shiftedrelative to the unsubstituted benzotriazoles, the absorbance is muchgreater as seen by the absorbance at λ max. In the following examplesthe absorbance at 375 nm is reported for 20 mg/l concentrations. This isnot the molar extinction values.

Compound* λ max nm ε @ λ max Absorbance @ 375 nm Q 345 16,500 0.28 U 36217,300 0.50 CC 359 14,100 0.42 S 348 15,000 0.35 BB 348 14,000 0.33 DD358 15,700 0.42 EE 328 20,700 0.03 *Q is2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole. U is5-phenylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.CC is5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-ocrylphenyl)-2H-benzotriazole.S is5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-ocrylphenyl)-2H-benzotriazole.BB is5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole. DDis 5carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.EE is 2-(2-hydroxy-5-trifluoromethylphenyl)-2H-benzotriazole.

It is noted that compound EE, prepared in Example 44, is closely relatedto the compounds disclosed in Japanese Sho 47-15210 and has poor redregion absorbance. This is an unwanted property for the UV absorberswhere absorbance in the upper regions (above 350 nm) of the UV spectraare of vital importance.

EXAMPLE 75 Yellowness Color Data

The following examples show the difference in color between some of theinstant compounds as measured by a Macbeth Color-Eye instrument at aconcentration of 30 mg/100 mL in butyl acetate. This shows the relativecolor of the benzotriazoles having various substituents in the5-position of the benzo ring and in the 3- and 5-positions of the phenylring. In the table, the compounds are listed by increasing b value. Theinstrument measures yellowness as b and DE is the correspondingYellowness Index value.

Compound* b DE Q −0.02   0.07 BB 0.20 0.27 FF 0.54 0.72 S 1.05 1.28 DD1.85 2.25 CC 2.84 3.35 U 3.75 4.42 *Q is2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole. U is5-phenylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.(see Example 5) CC is5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.(see Example 37) S is s is5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.(see

The compounds not having an α-cumyl moiety in the 3-position of thephenyl ring have better color than the compounds having such a group atthat position.

EXAMPLE 76 Yellowness Color Data

The following example shows the lower color in a polymer resincomposition containing benzotriazole substituted with a trifluoromethylgroup on the benzo ring compared to a similar benzotriazole substitutedby a sulfonyl moiety.

Test additives are dry blended with polycarbonate pellets (MAKROLON®2608-1000, Bayer) using a Turbula mixer. The dry blends are extruded andpelletized using a single screw extruder operated at 525-550° F.(274-288° C.). The pellets are dried overnight in a vacuum oven andmolded into test plaques (2″×2″×0125″) using an injection molderoperated at 525-550° F. (274-288° C.). The color of the test plaques aremeasured, as yellowness index values using ASTM D-1925, on ten plaquesusing a spectrophotometer and the average value reported as seen in thetable below.

Formulation* Yellowness Index 0.08% Phosphite 4.5 0.08% Phosphite plus7.9 0.3% UV absorber BB 0.08% Phosphite plus 7.4 0.3% UV absorber P

* Phosphite is tris(2,4-di-tert-butylphenyl) phosphite.

BB is5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole.(see Example 31)

P is 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole.

Additives are dry blended with polycarbonate pellets (LEXAN®141-111N,General Electric) using a turbula mixture. The dry blends are extrudedand pelletized using a single screw extruder operated at 525° F. (274°C.). The pellets are dried overnight in a vacuum oven and molded intotest plaques (2″×2″×0.125″) using an injection molder operated at525-550° F. (274-288° C.). The color of the test plaques as yellownessindex values is measured on eight plaques using a calorimeter and theaverage value reported below.

Formulation* Yellowness Index Unstabilized control 6.8 0.3% UV absorberP 8.2 0.3% UV absorber J 7.5 0.3% UB absorber GG 13.0  0.3%alkylsulfonyl benzotriazole 24.2  *P is2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole. J is2-(2-hyrdroxy-5-tert-octylphenyl-2H-benzotriazole. GG is5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl-2H-benzotriazole.

EXAMPLE 77

To ascertain the effect on thermal durability and loss rate from a highsolids thermoset acrylic coating of various 2H-benzotriazole UVabsorbers substituted by a variety of electron withdrawing and electrondonating groups, the following tests are carried out.

A high solids thermoset acrylic clear coat is prepared by mixing anexperimental acrylic polyol resin and hexamethoxymethylmelamine(Resimene® 747, Monsanto) at a solids ratio of 60/40. The dodecylbenzenesulfonic acid catalyst (Nacure® 5225; King Industries) is added at 0.70%by weight. A flow aid Modaflow® (Monsanto) is added at 0.25% by weightto form a model acrylic melamine resin system.

The model clear coat is reduced with xylene to a viscosity of 26-27second using a Zahn #2 cup and applied via a conventional air spray at50 psi (3.5 Kg/cm²) over a 1″×3″ (2.54 cm×7.62 cm) quartz slide. Cure isachieved by baking the slide for 30 minutes at 260° F. (127° C.). Theclear coat is stabilized with 1% by weight of a hindered amine lightstabilizer, bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,(TINUVIN® 123, Ciba-Geigy). The various test benzotriazole UV absorbersare incorporated at the 5 mmol % by weight in the clear coat. The filmthickness on the quartz slides range from 1.15 to 1.41 mils (0.029 to0.036 mm).

The films on the quartz slides are weathered according to the followingconditions in Xenon Arc Weather-Ometer with a controlled irradiance at6500 W, using inner quartz and outer borosilicate S-type filter. Theirradiation cycle is as follows: 40 minutes of straight iradiation withno water spray, followed by 20 minutes of light plus front spray,followed by 60 minutes of light irradiation and finally by 60 minutesdart plus rear spray (condensation). The setting is at 0.55 W/M² at 340nm, 1.98 kJ/hour. In the light cycle the black panel temperature iscontrolled at 70±2° C. The relative humidity in the light cycle is inthe range of 50-55% and in the dark cycle 100%. The absorbance of thelong wavelength UV band as a function of Xenon arc weathering hours arerecorded in the table below.

To follow the loss of UV absorbers from the clear coats, UV spectra aremeasured initially and after weathering at regular time intervals. TheUV spectrophotometer measures absorbance linearly up to 5.5 absorbanceunits using a reference beam attenuation technique.

It is assumed that the degradation products from the UV absorber do notcontribute to the UV spectrum. This is tested by following the ratio ofabsorbance of the band at about 300 nm and the band at about 340 nm. Theratio does not change upon weathering the sample. This suggests that theUV spectrum of the weathered films correspond to the amount of UVabsorber remaining in the film with very little if any contribution tothe spectrum by photo degradants.

The data in the table below are based on formula A after 1211 hours ofexposure of the clear coats containing the test benzotriazole UVabsorbers.

Units Absorbance Compound Loss G₂ E₁ E₂* A 1.7982 hydrogen -PO(OEt)₂tert-octyl B 1.6300 hydrogen nitro tert-octyl C 1.4863 phenyl-S-tert-butyl group I D 1.4002 hydrogen hydrogen group II E 1.1872 methoxytert-butyl methyl F 0.5259 hydrogen tert-butyl group II G 0.4527hydrogen hydrogen α-cumyl H 0.4420 hydrogen tert-butyl group I I 0.4299hydrogen tert-octyl α-cumyl J 0.4134 hydrogen hydrogen tert-octyl K0.3777 hydrogen tert-octyl tert-octyl L 0.3712 hydrogen tert-butylCH₂CH₂CH₂OH M 0.3433 hydrogen α-cumyl group II N 0.3098 cyano tert-butyltert-butyl O 0.2689 phenyl-SO₂- tert-butyl group I P 0.2576 hydrogenα-cumyl α-cumyl Q 0.2492 hydrogen α-cumyl tert-octyl *Group I isCH₂CH₂COOC₈H₁₇ Group II is CH₂CH₂COOCH₃

Inspection of these data leads to some clear conclusions about thephotostability of 2H-benzotriazole UV absorbers and about the nature ofthe substitution which will affect that photostability.

Increased photostability occurs when E₁ is α-cumyl or phenyl and when G₂is an electron withdrawing group such as phenyl-sulfonyl or cyano.

The nature of the E₂ group has less influence on the photostability ofthe benzotriazole UV absorbers.

From these observations, then an idealized benzotriazole UV absorbermight theoretically be designed where G₂ is an electron withdrawinggroup, E₁ is an effective bulky group, and E₂ is a thermally stablemoiety. One such idealized compound might be a benzotriazole where G₂ isphenylsulfonyl, E₁ is α-cumyl and E₂ is tert-octyl. This benzotriazoleis generically claimed in U.S. Pat. No. 5,280,124. The data given inExample 78 below confirms this prediction and this “idealized” compounddoes indeed exhibit a very low loss rate well below the present state ofthe art.

EXAMPLE 78

This example demonstrates the superior durability of benzotriazolessubstituted at the 5-position of the benzo ring.

Following the general procedure of Example 77, a number of additionalbenzotriazole test compounds are incorporated into a high solidsthermoset acrylic melamine resin at such concentrations between 1.93 and3 % by weight to give equal molar concentrations of test benzotriazolein equal film thickness, and sufficient to give a starting absorbance ofapproximately 2.0 absorbance units.

The test discs are exposed in a Xenon-Arc Weather-Ometer at X180 cycle(0.45 Watts/M²). The initial UV absorbance is measured followed bymeasurements at roughly 250 hour intervals for the first 2000 hours andevery 500 hours thereafter. Each clear coat also contains 1 % by weightof a hindered amine light stabilizer,bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, as well.

The data in the table below are based on compounds of formula A after1253 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers.

Units Absorbance Compound Loss G₂ E₁ E₂ R 0.2424 hydrogen phenyl α-cumylQ 0.2351 hydrogen α-cumyl tert-octyl S 0.1271 CF₃ α-cumyl tert-octyl T0.1827 phenyl-SO₂ tert-butyl tert-butyl

The data in the table below are based on compounds of formula A after1489 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers.

Units Absorbance Compound Loss G₂ E₁ E₂ R 0.3724 hydrogen phenyl α-cumylQ 0.287  hydrogen α-cumyl tert-octyl S 0.1547 CF₃ α-cumyl tert-octyl T0.2654 phenyl-SO₂ tert-butyl tert-butyl

The data in the table below are based on compounds of formula A after2521 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers.

Units Absorbance Compound Loss G₂ E₁ E₂ R 0.4824 hydrogen phenyl α-cumylQ 0.4054 hydrogen α-cumyl tert-octyl S 0.2192 CF₃ α-cumyl tert-octyl T0.3570 phenyl-SO₂ tert-butyl tert-butyl

It is clear from the three tables above that Compounds S and especiallyT which have an electron withdrawing group at the 5-position of thebenzo ring are significantly more durable than benzotriazoles which donot have such a group on the benzo ring.

The data in the table below are based on compounds of formula A after1264 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers.

Units Absorbance Compound Loss G₂ E₁ E₂ Q 0.2293 hydrogen α-cumyltert-octyl S 0.0921 CF₃ α-cumyl tert-octyl T 0.1965 phenyl-SO₂tert-butyl tert-butyl U 0.0944 phenyl-SO₂ α-cumyl tert-octyl V 0.1719chloro α-cumyl tert-octyl W 0.1655 fluoro α-cumyl tert-octyl X 0.1796hydrogen phenyl tert-octyl

The data in the table below are based on compounds of formula A after1518 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers.

Units Absorbance Compound Loss G₂ E₁ E₂ Q 0.2662 hydrogen α-cumyltert-octyl S 0.1116 CF₃ α-cumyl tert-octyl T 0.2423 phenyl-SO₂tert-butyl tert-butyl U 0.1114 phenyl-SO₂ α-cumyl tert-octyl V 0.1955chloro α-cumyl tert-octyl W 0.1668 fluoro α-cumyl tert-octyl X 0.2220hydrogen phenyl tert-octyl

The data in these tables clearly show that benzotriazoles substituted byan electron withdrawing group on the benzo ring, particularly a groupsuch as trifluoromethyl, fluoro or phenylsulfonyl, are especiallydurable as measured by low loss rate absorbance values after exposure toactinic radiation. Compounds S, U, V and W are especially durable andfit the profile proposed above. Indeed, the prediction that Compound Uwould be particularly durable is borne out by the data above. Inspectionof the data for compounds T and U shows the added beneficial effect ofhaving an effective bulky group such as α-cumyl at the R₁ positioncompared to a mere alkyl moiety such as tert-butyl at that position.

EXAMPLE 79

This example demonstrates the lack of durability of a representativebenzotriazole substituted by an electron donating group on the phenoxyring relevant to a commercial benzotriazole in a coating composition.

Following the general procedure of Example 77, representativebenzotriazole test compounds are incorporated into a high solidsthermoset acrylic melamine resin at concentrations between 1.93 and 3%by weight to give equal molar concentrations of the test benzotriazolein equal film thickness and sufficient to give a starting absorbance ofapproximately 2.0 absorbance units. The test samples are exposed asdescribed in Example 77 for 1002 hours.

Compound* Units of Absorbance Loss Q 0.28 Z 1.58 *Q is2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole. Z is2-(2-hydroxy-4-n-butoxyphenyl)-2H-benzotriazole.

It is clear that the presence of an electron donating group on thephenoxy ring of the benzotriazole adversely affects the durability ofsaid benzotriazole.

EXAMPLE 80

The durability of representative benzotriazoles in thermoplasticsubstrates is determined by incorporating various test compounds intosolvent cast films of poly(vinyl chloride), polycarbonate andpolystyrene resins. The free standing films are mounted into cardboardholders, secured in metal frames and exposed in an Atlas C165 Xenon-arcWeather-Ometer under dry conditions according to ASTM G26 for 1100 and2200 hour exposure. Loss of UV absorber is determined by monitoring theloss of diagnostic UV absorption as described earlier. Performance ismeasured by a change in color or the physical integrity of the film.

Polycarbonate flake (LEXAN® 145, General Electric) is dissolved inmethylene chloride at room temperature along with between 1 and 3% byweight of test benzotriazole, based on the polycarbonate. Films are castusing a calibrated drawdown bar to prepare 1 mil thick film afterdrying.

The following test data show the increase in durability obtained with abenzotriazole substituted on the 5-position of the benzo ring with analkylsulfonyl moiety. These results mirror those obtained with coatingresults.

Absorbance (max) Compound* (wt %) 0 hrs 1100 hrs Loss units % Loss AA(2.5) 1.333 1.300 0.033  2.5 (364 nm) P (1.5) 1.062 0.919 0.143 13.5(347 nm) P (2.5) 2.104 1.844 0.260 12.3 *AA is5-nonylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.P is 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotrizole.

EXAMPLE 81

Following the procedure of Example 80, this example shows the increasein polycarbonate film of the durability of a benzotriazole substitutedon the benzo ring with a trifluoromethyl moiety in the 5-position afterexposure for 2000 hours in the Atlas C165 Weather-meter.

Absorbance (max) Compound* (wt %) 0 hrs 2000 hrs Loss units % Loss BB(2.19) 2.654 2.638 0.016 0.6 (352 nm) J (1.81) 2.454 2.270 0.184 7.5(344 nm) *BB is5-trifluoromethyl-2-(2-hydroxy-5tert-octylphenyl)-2H-benzotriazole.(compound of Example 31). J is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotnazole.

EXAMPLE 82

The data in the following example show the change in color of thepolycarbonate films exposed according to the procedure of Example 81 asmeasured on an ACS spectrophotometer, large area view, spectralcomponent included d/8, 10° observer, with yellowness index measuredaccording to ASTM D 1925 after 2000 hours exposure.

These data correlates with the advantages seen for the instant compoundin terms of stability and spectral coverage leading to a direct increasein performance of the polycarbonate resin films.

Compound* (wt %) Δ Yellowness Index BB (2.19) 2.9 J (1.18) 4.0 *BB is5-trifluoromethyl-2-(2-hydroxy-5tert-octylphenyl)-2H-benzotriazole.(compound of Example 31). J is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole.

The test compound BB is discernibly less colored than the prior artcompound J.

EXAMPLE 83

The following example shows that the stability increases observed forbenzotriazoles bearing an electron withdrawing group in the 5-positionof the benzo ring in polar coatings such as thermoset acrylic melamineresins and polycarbonate are also seen in less polar substrates such aspoly(vinyl chloride) (PVC).

PVC films of GEON® 27 (Geon Co.) are solvent cast as described abovewith warm tetrahydrofuran (THF) and exposed in an Atlas C165Weather-Ometer as described in Example 60 for 1100 hours.

Absorbance (max) Compound* (wt %) 0 hrs 1100 hrs Loss units % Loss AA(2.5) 1.149 1.103 0.036 3.1 (368 nm) P (1.5) 1.145 1.022 0.123 10.7 (347 nm) P (2.5) 2.211 2.081 0.130 5.6 *AA is5-nonylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.P is 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotnazole.

EXAMPLE 84

The following example shows an improvement in color protection of apigmented polyacetal formulation for a benzotriazole substituted on the5-position of the benzo ring with a trifluoromethyl moiety.

The test additives are dry blended with polyacetal pellets (DELRIN® 500PNC010, DuPont) using a Turbula mixer. The dry blend is extruded andpelletized using a twin screw extruder at a melt temperature of about410° F. (210° C.). The pellets are molded into test plaques(2″×2″×0.060″) using an injection molder operated at 410-420° F.(204-216° C.). The plaques are exposed in a Xenon-arc Weather-Ometeraccording to automotive test procedure SAE J1885. Exposure is measuredin terms of the total irradiation, measured in kilojoules per squaremeter (kJ/m²). Color change in the exposed samples is determined bymeasuring the color of the exposed samples compared to the unexposedsamples as color difference (AE) according to ASTM D2244. The contentsare in weight %.

Contents* Control Test Sample Polyacetal 98.8% 98.8% Pigment(CHROMOPHTAL ® Red G) 0.30% 0.30% Hindered Amine 0.25% 0.25%Benzotriazole P 0.60% — Benzotriazole S — 0.60% ACRAWAX C 0.05% 0.05%Color Difference (ΔE) after 600 kJ/m² 6.8 5.8 after 900 kJ/m² 11.7 10.0after 1240 kJ/m² 22.5 20.0 *Hindered amine isdi(1,2,2,6,6-pentamethylpiperidin-4-yl)2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate. P is2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole. S is5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.

EXAMPLE 85

The following examples illustrates the superior performance of abenzotriazole substituted on the 5-position of the benzo ring with atrifluoromethyl group in protecting poly(butylene terephthalate) asmeasured by gloss retention.

The test additives are dry blended with poly(butylene terephthalate)pellets (VALOX® 315-1001, General Electric) using a Turbula mixer. Thedry blends are extruded and pelletized using a twin screw extruder at465-490° C. The pellets are molded into test plaques (2″×2″×0.060″)using an injection molder operated at 475-515° F. (246-268° C.). Theplaques are exposed in a Xenon arc Weather-Ometer according to ASTM G26test method A. Gloss is measure at 60° on the unexposed and exposedsamples using a glossmeter according to ASTM D523. Gloss retention%=(gloss exposed sample/gloss of unexposed sample)×100. The contents arein weight %.

Contents* Control Test Sample Poly(butylene 98.35% 98.35% terephthalate)Titanium Dioxide 1.00% 1.00% Hindered Phenol 0.05% 0.05% Phosphite 0.10%0.10% Benzotriazole P 0.50% — Benzotriazole S — 0.60% Gloss Retention %after 500 hrs exposure 89% 94% after 750 hrs exposure 65% 82% *Hinderedphenol is 3,5-dioxaoctamethylenebis(3-methyl-5-ter-butyl-4-hydroxy-hydrocinnamate). Phosphite istris(2,4-di-tert-butylphenyl)phosphite. P is2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole. S is5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.

EXAMPLE 86

Polystyrene films (crystalline polystyrene obtained from Chevron, freeof zinc stearate and mineral oil) are solvent case from solutions inmethylene chloride. These films are exposed to UV light as described inExample 80. The samples contain no hindered amine stabilizer and aremonitored for color change after 1000 hours exposure, for loss of UVabsorber and for physical integrity (cracking or catastrophic filmfailure). Exposure is stopped after 1500 hours.

Exposure 1000 hours and 1500 hours Compound* (wt %) Yellowness IndexFilm Integrity Compound of 6.2 film intact Example 31 (2.19%) Compound A6.9 film failed Compound P 9.2 film cracking *Compound A is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole. Compound P is2-(2-hydroxy-3,5-diα-cumylphenyl)-2H-benzotriazole.

Products from the polystyrene degradation absorbed in the ultravioletobscuring attempts at UV absorber measurements. Color data obtainedafter 1000 hours exposure show the effectiveness of the instant compoundof Example 31. After 1500 hours exposure, the films containing compoundsA and P show significant film degradation while the film containing theinstant compound of Example 31 is still intact.

EXAMPLE 87

Polycarbonate films of about 1 mil thickness and containing a UVabsorber are prepared by dissolving polycarbonate granules (LEXAN® 145,General Electric) and UV absorbers in methylene chloride and casting thefilms on a glass plate using a drawdown bar. The films are exposed for2000 hours in a Xenon Arc Weather-O-meter according to ASTM G26 testmethod C and the color change (ΔYI) versus that for unexposed films arerecorded.

Sample* (5% by weight) ΔYI Compound B 6.0 Compound of Example 43 4.4*Compound B is2,2′-Methylene-bis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol].Compound of Example 43 is2,2′-Methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)4-tert-octylphenol].

The instant compound provides discernibly better color to thepolycarbonate composition than Compound B.

EXAMPLE 885-Trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole

When using the general procedure of Example 1 the2-α-cumyl-4-tert-octylphenol is replaced by2-α-cumyl-4-(2-hydroxyethyl)phenol, the title compound is prepared.

What is claimed is:
 1. A composition stabilized against thermal,oxidative or light-induced degradation which comprises (a) an organicmaterial subject to thermal, oxidative or light-induced degradation, and(b) an effective stabilizing amount of a compound of formula I, III orIV

wherein G₁ is hydrogen or chloro, G₂ is cyano, perfluoroalkyl of 1 to 12carbon atoms or fluoro, G₆ is perfluoroalkyl of 1 to 12 carbon atoms, G₇is hydrogen or perfluoroalkyl of 1 to 12 carbon atoms, E₁ is hydrogen,straight or branched chain alkyl of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms; or E₁ is alkyl of 1 to 24 carbon atomssubstituted by one or two hydroxy groups, E₂ and E₂′ are independentlystraight or branched alkyl chain of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by one tothree alkyl of 1 to 4 carbon atoms; or E₂ and E₂′ are independently saidalkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atomssubstituted by one or more —OH, —OCOE₁₁, —OE₄, —NCO, —NH₂, —NHCOE₁₁,—NHE₄ or —N(E₄)₂, or mixtures thereof, where E₄ is straight or branchedchain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenylinterrupted by one or more —O—, —NH— or —NE₄—groups or mixtures thereofand which can be unsubstituted or substituted by one or more —H, —OE₄ or—NH₂ groups or mixtures thereof; n is 1 or 2, when n is 1, E₅ is OE₆ orNE₇E₈, or E₅ is —PO(OE₁₂)₂, —OSi(E₁₁)₃ or —OCO—E₁₁, or straight orbranched chain C₁-C₂₄alkyl which is interrupted by —O—, —S— or —NE₁₁ andwhich can be unsubstituted or substituted by —OH or —OCO—E₁₁, C₅-C₁₂cycloalkyl which is unsubstituted or substituted by —OH, straight chainor branched C₂-C₁₈alkenyl which is unsubstituted or substituted by —OH,C₇-C₁₅aralkyl, —CH₂—CHOH—E₁₃ or glycidyl, E₆ is hydrogen, straight orbranched chain C₁-C₂₄alkyl which is unsubstituted or substituted by oneor more OH, OE₄ or NH₂ groups, or —OE₆ is —(OCH₂CH₂)_(w)OH or—(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12 and E₂₁ is alkyl of 1 to 12 carbonatoms, E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or E₇ and E₈ together with the N atom are a pyrtolidine, piperidine,piperazine or morpholine ring, E₅ is —X—(Z)_(p)—Y—E₁₅ wherein X is —O—or —N(E₁₆)—, Y is —O— or —N(E₁₇)—, Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkyleneinterrupted by one to three nitrogen atoms, oxygen atoms or a mixturethereof, or is C₃-C₁₂-alkylene, butenylene, butynylene, cyclohexylene orphenylene, each substituted by a hydroxyl group, m is zero, 1 or 2, p is1, or p is also zero when X and Y are —N(E₁₆)— and —N(E₁₇)—,respectively, E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—,forms together with E₁₇ a group —CO—CH═CH—CO—), wherein E₁₈ is hydrogenor methyl, and E₁₉ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ ishydrogen, C₁-C₁₂-alkyl or a group of the formula

wherein the symbols E₁, G₂, X, Z, m and p have the meanings definedabove, and E₁₆ and E₁₇ independendy of one another are hydrogen,C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms, or iscyclohexyl or C₇-C₁₅aralkyl, and E₁₆ together with E₁₇ in the case whereZ is ethylene, also forms ethylene, when n is 2, E₅ is one of divalentradicals —O—E—O— or —N(E₁₁)—E₁₀—N(E₁₁)—, E₉ is C₂-C₈alkylene,C₄-C₈alkenylene, C₄alkynylene, cyclohexylene, straight or branched chainC₄-C₁₀alkylene which is interrupted by —O— or by—CH₂—CHOH—CH₂—O—E₁₄—O—CH₂—CHOH—CH₂—, E₁₀ being straight or branchedchain C₂-C₁₂alkylene which may be interrupted by —O—, cyclohexylene, or

or E₁₀ and E₁₁ with the two nitrogen atoms form a piperazine ring, E₁₄is straight or branched chain C₂-C₈alkylene, straight or branched chainC₄-C₁₀alkylene which is interrupted by —O—, cycloalkylene, arylene or

where E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms or E₇ and E₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene, E₁₁ is hydrogen, straight or branched chainC₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, straight or branched chain C₂-C₁₈alkenyl,C₆-C₁₄aryl or C₇-C₁₅aralkyl, E₁₂ is straight or branched chainC₁-C₁₈alkyl, straight or branched chain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl,C₆-C₁₆aryl or C₇-C₁₅aralkyl, E₁₃ is H, straight chain or branchedC₁-C₁₈alkyl which is substituted by —PO(OE₁₂)₂, phenyl which isunsubstituted or substituted by OH, C₇-C₁₅aralkyl or —CH₂OE₁₂, L isalkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms,benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylylene orcycloalkylidene, and with the proviso that when G₂ is CF₃ and E₁ ishydrogen, E₂ is not methyl.
 2. A composition according to claim 1wherein component (b) is a compound of formula I

wherein G₁ is hydrogen, G₂ is cyano, CF₃— or fluoro, E₁ is phenylalkylof 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkylsubstituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms, straightor branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is said alkyl of 1 to 24 carbonatoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more—OH, —OCOE₁₁, —OE₄, —NCO, —NH₂, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixturesthereof, where E₄ is straight or branched chain alkyl of 1 to 24 carbonatoms; or said alkyl or said alkenyl interrupted by one or more —O—,—NH—or —NE₄— groups or mixtures thereof and which can be unsubstitutedor substituted by one or more —OH, —OE₄ or —NH₂ groups or mixturesthereof; or is a compound of formula I wherein, G₁ is hydrogen, G₂ isCF₃-or fluoo, E₁ is hydrogen or straight or branched alkyl of 4 to 24carbon atoms, and E₂ is as defined above.
 3. A composition according toclaim 1 wherein the compound of formula III is a compound of formulaIIIA

wherein G₁ is hydrogen, G₂ is is CF₃— or fluoro, E₁ is hydrogen,straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7to 15 carbon atoms, E₅ is —OE₆ or —NE₇E₈, or E₅ is —X—(Z)_(p)—Y—E₁₅wherein X is —O— or —N(E₁₆)—, Y is —O— or —N(E₁₇)—, Z isC₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to three nitrogenatoms, oxygen atoms or a mixture thereof, or is C₃-C₁₂-alkylene,butenylene, butynylene, cyclohexylene or phenylene, each substituted bya hydroxyl group, m is 0, 1,2or3, p is 1, or p is also zero when X and Yare —N(E₁₆)— and —N(E₁₇)—, respectively, E₁₅ is a group—CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—, forms together with E₁₇ agroup —CO—CH═CH—CO—, wherein E₁₈ is hydrogen or methyl, and E₁₉ ishydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ is hydrogen, C₁-C₁₂-alkyl ora group of the formula


4. A composition according to claim 3 wherein component (b) is acompound of formula IV

wherein G₆ is CF₃, G₇ is hydrogen or CF₃, E₂ and E₂′ are independentlystraight or branched alkyl chain of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; and L is alkylene of 1 to 12 carbon atoms,alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene,α,α,α′,α′-tetramethyl-m-xylylene or cycloalkylidene.
 5. A compositionaccording to claim 2 wherein component (b) is a compound of formula I

wherein G₁ is hydrogen, G₂ is CF₃—, E₁ is phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms, E₂ is straight orbranched alkyl chain of 1 to 24 carbon atoms, straight or branched chainalkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or saidphenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4carbon atoms; or E₂ is said alkyl of 1 to 24 carbon atoms or saidalkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE₁₁,—NH₂ or —NHCOE₁₁, or mixtures thereof, or said alkyl or said alkenylinterrupted by one or more —O— and which can be unsubstituted orsubstituted by one or more —OH, or is a cosmpound of formula I wherein,G₁ is hydrogen, G₂ is CF₃—, E₁ is hydrogen, straight or branched alkylof 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and E₂is as defined above.
 6. A composition according to claim 3 wherein thecompound of formula III is a compound of formula IIIA

wherein G₁ is hydrogen, G₂ is CF₃—, E₁ is hydrogen, straight or branchedalkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, E₅is —OE₆ or —NE₇E₈ where E₆ is hydrogen, straight or branched chainC₁-C₂₄alkyl which is unsubstituted or substituted by one or more OHgroups, or —OE₆ is —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1to 12 and E₂₁ is alkyl of 1 to 12 carbon atoms, and E₇ and E₈ areindependently hydrogen, alkyl of 1 to 18 carbon atoms, straight orbranched chain C₃-C₁₈alkyl which is interrupted by —O—, —S— or —NE₁₁—,C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇ and E₈together with the N atom are a pyrrolidine, pipeidine, piperazine ormorpholine ring.
 7. A composition according to claim 3 wherein component(b) is a compound of formula IV

wherein G₆ is CF₃, G₇ is hydrogen or CF₃, E₂ and E₂′ are independentlystraight or branched alkyl chain of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; and L is methylene.
 8. A compositionaccording to claim 3 wherein component (b) is (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-ctylphenyl)-2H-benzotriazole;(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;(c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tertoctylphenyl)-2H-benzotriazole;(d)2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol];(e)methylene-2-[4-tert-ctyl-6-(2H-benzotriazol-2-yl)phenol]2′-[4-tert-octyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];(f)3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicacid; (g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;(h) isooctyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;(i)5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;(j)5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole;(k)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;(l)5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzotriazole;(m)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole;(n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;(o)5-trifluoromethyl-2-(2-hydroxy-3-αoumyl-5-nonylphenyl)2H-benzotriazole;(p)5-trfluormethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(q)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole; (r)5-trifluoromethyl-2-(2-hydroxy-3,5ditert-amylphenyl)-2H-benzotriazole;(s)5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole;(t)5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;(u)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;(v)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(w)5-tiitluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(x)5-trifluoromethyl-2-(2-hydroxy-3,5di-α-cumylphenyl)-2H-benzotriazole; or(y) 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole.
 9. Acomposition according to claim 1 wherein the organic material is anatural, semi-synthetic or synthetic polymer or a polymer blend or acopolymer.
 10. A composition according to claim 9 wherein the polymer isa polyolefin, polycarbonate, a styrenic, ABS, a nylon (polyamide), apolyester, a polyurethane, a polyacrylate, a rubber modified styrenic,poly(vinyl chloride), poly(vinyl butyral), polyacetal(polyoxymethylene), poly/ethylene/1,4-cyclohexylenedimethyleneterephthalate (PETG) or an ethylene/acrylic acid copolymer or saltsthereof.
 11. A composition according to claim 10 wherein the polymer isa polyester.
 12. A composition according to claim 11 wherein thepolyester is poly(ethylene terephthalate), poly(butylene terephthalate)or poly(ethylene naphthalenedicarboxylate), or copolymerpoly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETG.
 13. Acomposition according to claim 9 wherein the polymer is a thermoplasticpolymer.
 14. A composition according to claim 10 wherein the polymer isis a polyolefin or polycarbonate.
 15. A composition according to claim14 wherein the polymer is polyethylene or polypropylene.
 16. Acomposition according to claim 15 wherein the polymer is polypropylene.17. A composition according to claim 1 which additionally contains aneffective stabilizing amount of at least one other UV absorber selectedfrom the group consisting the benzotriazoles, the s-triazines,hydroxy-benzophenones, the α-cyanoacrylates, the oxanilides andbenzoates.
 18. A composition according to claim 17 wherein the other2-hydroxyphenyl-2H-benzotriazole is selected from the group consistingof 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole;2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole;2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole;2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole;2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-ocma(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;and 2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotniazole.
 19. A composition according to claim 18 wherein the otherbenzotriazole is 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyll-2H-benzotriazole;2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotnazole;2-(2-hydroxy-5-tert-ctylphenyl)-2H-benzotriazole; or2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.20. A composition according to claim 1 which also contains an effectivestabilizing amount of a hindered amine.
 21. A composition according toclaim 10 wherein the polymer is a copolymer of ethylene/acrylic acid oran alkali metal, alkaline earth metal or transition metal salt thereof.